Fatty acids, soaps, surfactant systems, and consumer products based thereon

ABSTRACT

Novel fatty acids and derivatives thereof such as salts, new surfactant systems comprising one or more of these compounds, consumer products such as laundry products, personal care products, pharmaceutical compositions, industrial cleaners, and the like comprising said compounds or surfactant systems.

CROSS REFERENCE

[0001] This is a divisional of U.S. application Ser. No. 09/507,823,filed on Feb. 22, 200, which is a continuation under 35 USC §120 of PCTInternational Application Serial No. PCT/US98/22054, filed Oct. 19,1998; which claims priority to Provisional Application Serial No.60/063,603, filed Oct. 23, 1997.

FIELD OF THE INVENTION

[0002] The present invention relates to certain novel fatty acids andderivatives thereof such as salts, to new surfactant systems comprisingone or more of these compounds, and to consumer products such as laundryproducts, personal care products, pharmaceutical compositions,industrial cleaners, and the like comprising said compounds orsurfactant systems.

BACKGROUND OF THE INVENTION

[0003] Fatty acids and soaps have a long history tracing into antiquity.The art was highly advanced at the turn of the last century (See, forexample, “Modern Soaps, Candles and Glycerin”, L. L. Lamborn, VanNostrand, New York, 1906). Weighty tomes such as “Industrial Oil and FatProducts”, A. E. Bailey, Interscience, New York, 1951 and “Fatty Acids”,Ed. Klare S. Markley, Parts 1-5, Interscience, N.Y., 1960-1968 provide asystematic entry-point to the art. “Fatty Acids”, Ed. E. H. Pryde,American Oil Chemists' Society, 1979, discusses fatty acids includingsome mention of branched types. Structures, separations and synthesis offatty acids, including some branched examples, are laid out by F. D.Gunstone in “An Introduction to the Chemistry and Biochemistry of FattyAcids and their Glycerides”, Chapman and Hall, London, 1958. Substantialcontributions to methods of synthesis of branched fatty acids were madeby James Cason; see, for example, J. Amer. Chem. Soc., Vol. 66, (1944),p.46. Certain branched mixed fatty acids with high levels of impuritieswere known in wartime Germany, and have several disadvantages. SeeBailey cited supra at pages 504-506.

[0004] Fatty acids, including branched types, can be isolated fromnaturally occurring materials such as vegetable, animal, fish, bird orinsect oils or bacteria and can be isolated from human skin lipids.Likewise they can be made from petrochemical starting-materials.

[0005] Naturally occurring complex mixtures of esters which in principlecan be hydrolyzed to fatty acid mixtures for example include thosedisclosed by Juarez et al, Archives of Biochemistry and Biophysics, Vol.293, pp. 331-341 (1992); by Nicolaides et al in Biomedical MassSpectrometry, Vol. 4., pp. 337-47 (1977); and by Ratnayake et al inLipids, Vol. 24, pp 630-637 (1989). See also Nicolaides et al., Lipids,Vol. 6., pp. 901-905 (1971). Though such disclosures typically identifynumerous monomethyl or polymethyl branched fatty acid derivatives asbeing present in natural systems, useful amounts of individual compoundsare typically not secured.

[0006] Fatty acids and their derivatives, including certain branchedtypes, have an enormous utility to man and have been used inapplications ranging from laundry cleaning agents to anticonvulsivedrugs, dermal lotions and cosmetics. See, for example, commonly assignedWO 94/12608 published Jun. 9, 1994. Such derivatives can havelimitations, for example off-odors; further, it has not always beenrecognized which structures (e.g., primary or secondary carboxyl) are ofgreatest utility. Some branched fatty acids, more particularly, havebeen shown to have unusual properties, such as low melting pointsrelative to equal carbon number linear analogs. In view of the age andextent of the art, improvements are becoming more difficult to achieveand what at first may appear to be small advances may carry greatweight.

[0007] Commercially described branched fatty acids of varyingavailability include a few from Exxon, Shell, Henkel, Sasol and others;see the technical publications of these suppliers. Many of suchmaterials contain quaternary carbon atoms. Perhaps the most commonbranched fatty acid type useful as a surfactant but too costly andlimited in availability for high-volume applications and moreover,lacking in formulation flexibility, is isostearic acid; there are alsosome short-chain types, for example 2-ethylhexanoic acid, but these arerelatively unuseful as surface-active agents. In short, there is asevere limitation in flexibility to the formulator when this handful ofcurrently commercial types of branched fatty acid or mixture is reliedon.

[0008] There is therefore an ongoing need for improvement in the fieldof branched fatty acid compositions. Accordingly, it is an object hereinto provide such improvements, particularly novel fatty acids, soaps andderivatives, especially those capable of improving one or more of thefollowing technological systems: surfactants and surfactant systems;cosurfactants; builders; antifoams; emollients and skin feel agents;particularly important is to accomplish improvements useful for theformulator of consumer products such as personal care products andlaundry and cleaning products.

BACKGROUND ART

[0009] As noted, certain branched-chain fatty acids have been known forsome time in the art. See, for example, “Fatty Acids (Branched-Chain)”in Kirk-Othmer's Encyclopedia of Chemical Technology, 1st. Edition,(1951), Interscience Publishers, Vol. 6, at pages 262-266, WO9807680,WO9807679 and references cited therein including, for example, severalpapers by Cason et al.

[0010] Known branched-chain fatty acids (for example those recognized byChemical Abstracts by Registry numbers or those which can be found bymanual searching of the older Chemical Abstracts) are nonlimitinglyillustrated by:

[0011] 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-methyldecanoic acid; 2-, 3-, 4-,5-, 6-, 7-, 8-, 9-and 10-methylundecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-,8-, 9-, 10- and 11-methyldodecanoic acid; 2-, 3-, 4-, 5-, 8-, 9-, 11-and 12-methyltridecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,12- and 13-methyltetradecanoic acid; 2-, 3-, 4-, 6-, 7-, 10-, 11-, 12-,13- and 14-methylpentadecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-,10-, 11-, 12-, 13-, 14- and 15-methylhexadecanoic acid; 2-, 3-, 4-, 5-,6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15- and 16-methylheptadecanoicacid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16-and 17-methyloctadecanoic acid; 2-, 3-, 4-, 10-, 17- and18-methylnonadecanoic acid.

[0012] In particular with respect to the above compounds,11-methylpentadecanoic acid, 8-methyloctadecanoic acid and14-methyloctadecanoic acid have been disclosed in U.S. Pat. No.4,997,456 and commonly assigned U.S. Pat. Nos. 4,000,340 and 4,076,633disclose 15-methyloctadecanoic acid.

[0013] Also known in the art and identified by Chemical Abstractsthrough registry numbers or locatable in early Chemical Abstracts are:2,2-, 2,3-, and 2,4-dimethyldecanoic acid; 2,2-, 2,3-, 2,4-, 2,6- and2,8-dimethylundecanoic acid; 2,2-, 2,3-, 2,4-, 2,6-, 2,8- and2,10-dimethyldodecanoic acid; 2,4-, 2,5-, 2,6-, 2,8- and2,10-dimethyltridecanoic acid; 2,2-, 2,3-, 2,4-, 2,6-, 2,8-, and2,10-dimethyltetradecanoic acid, 2,4-, 2,6-, 2,10-, 2,12- and2,14-dimethylpentadecanoic acid; 2,2-, 2,4-, 2,6-, 2,10-, 2,12- and2,14-dimethylhexadecanoic acid; 2,2-, 2,4-, 2,5-, 2,6- and2,10-dimethylheptadecanoic acid; 2,2-, 2,3-, 2,4- and2,9-dimethyloctadecanoic acid; and 2,2-dimethylnonadecanoic acid.

[0014] Also known in the art and identified by Chemical Abstractsthrough registry numbers or locatable in early Chemical Abstracts are:3,3-, 4,4- and 5,9-dimethyldecanoic acid; 3,3-, 3,5-, 3,7-, 3,9-, 4,8-,9,9- and 10,10-dimethylundecanoic acid; 3,3-, 3,5-, 3,7-, 3,9-, 3,11-,4,8- and 4,10-dimethyldodecanoic acid; 3,3-, 3,4-, 3,5-, 3,7-, 3,9-,3,11-, 4,8-, 5,7-, 10,10-and 12,12-dimethyltridecanoic acid; 3,3-, 3,5-,3,7-, 3,9-, 3,11-, 4,4-, 4,8-, 5,7-, 5,9-, 6,10-, 7,8-, 6,12-, 6,13-,8,8-, 9,13-and 10,13-dimethyltetradecanoic acid; 3,3-, 3,5-, 3,6-, 3,7-,3,9-, 3,11-, 3,13-, 4,8-, 4,10-, 5,9-, 6,8-, 6,10-and14,14-dimethylpentadecanoic acid; 3,3-, 3,7-, 4,8-, 4,10-, 4,14-, 5,9-,6,12-, 7,9-, 8,12-, 8,14-, 11,15-and 15,15-dimethylhexadecanoic acid;3,3-, 5,9-, 8,10- and 12,16-dimethylheptadecanoic acid; 3,3-, 7,9-,9,10-, 9,11- and 17,17-dimethyloctadecanoic acid; and3,3-dimethylnonadecanoic acid. In a few cases, the acids must beextracted from natural mixtures of fatty esters.

[0015] As referred to in Kirk Othmer's article supra, other branchedfatty acids known in the literature include: 2,9-dimethyloctadecanoicacid, 14-ethylhexadecanoic acid, 15-ethylheptadecanoic acid, and12-n-hexyloctadecanoic acid. There are also numerous known examples ofbranched fatty acids containing quaternary carbon atoms, for example,any of the known 2,2-dimethyl substituted long-chain fatty acidsspecifically named hereinabove.

[0016] The known trimethyl-substituted fatty acids, having chemicalabstracts registry numbers, include: 2,5,9-trimethyldecanoic acid;2,4,5-, 2,4,6- and 2,6,10-trimethylundecanoic acid; 2,4,6-, 2,4,8-,2,6,10- and 3,7,11-trimethyldodecanoic acid; 4,8,12-, 3,7,9-, 3,5,9-,2,4,10-, 2,4,8-, 2,4,6-, 2,6,10- and 4,8,12-trimethyltridecanoic acid;2,4,6-, 2,4,8-, 2,6,10-, 3,6,13-, 3,7,9-, 3,7,11- and5,9,13-trimethyltetradecanoic acid; 2,4,6-, 2,4,8-, 3,4,7-, 3,5,9-,3,7,9-, 3,7,11-, 3,9,11-, 3,14,14- and 6,10,14-trimethylpentadecanoicacid; 2,3,4- and 2,4,8-trimethylhexadecanoic acid;4,8,12-trimethylheptadecanoic acid; 2,4,8-trimethyloctadecanoic acid;and 4,8,12-trimethyloctadecanoic acid.

[0017] The known polymethyl-substituted fatty acids include:2,4,6,8-tetramethylundecanoic acid; 2,4,6,8,10-pentamethyldodecanoicacid; 3,7,9,11- and 3,5,9,11-tetramethyltridecanoic acid;2,2,4,6,8,10-hexamethyltridecanoic acid; 3,9,11,13-, 3,7,11,13-,3,7,9,11-, 2,4,6,10-, 3,5,11,13-, 3,5,9,11-, 2,4,8,10- and3,3,12,12-tetramethyltetradecanoic acid;2,6,10,14-tetramethylpentadecanoic acid; 2,6,10,14- and3,7,11,15-tetramethylhexadecanoic acid;4,8,12,16-tetramethylheptadecanoic acid;5,7,13,17-tetramethyloctadecanoic acid; and2,2,17,17-tetramethyloctadecanoic acid.

[0018] Known monoethyl-substituted fatty acids include: 2-, 4- and6-ethyldecanoic acid; 2-ethylundecanoic acid; 2-, 4-, 6- and10-ethyldodecanoic acid; 2-ethyltridecanoic acid; 2-, 4- and6-ethyltetradecanoic acid; 4- and 13-ethylpentadecanoic acid;2-ethylhexadecanoic acid; 2- and 15-ethylheptadecanoic acid; 2-, 3-, 9-,12- and 16-ethyloctadecanoic acid; and 2-ethylnonadecanoic acid.

[0019] Known monopropyl-substituted fatty acids include:2-propyldecanoic acid, 2- and 3-propylundecanoic acid; 2- and6-propyldodecanoic acid; 2-propyltridecanoic acid; 2- and3-propyltetradecanoic acid; 2- and 3-propylpentadecanoic acid; 2-, 3-and 4-propylhexadecanoic acid; 2-propylheptadecanoic acid; and2-propyloctadecanoic acid.

[0020] Other known substituted fatty acids include 2-ethyl-6-ethyl,2,2-diethyl and 2-ethyl-6-methyldecanoic acid; 2-ethyl-6,8-dimethyl,2-ethyl-4,6-dimethyl and 2-ethyl-6-methylundecanoic acid;2-ethyl-4,6,10-trimethyl, 2-ethyl-6,10-dimethyl, 2-ethyl-6,8-dimethyl,2-ethyl-4,6-dimethyl and 2-ethyl-6-methyldodecanoic acid;2,8-diethyl-12-methyl, 2-ethyl-12-methyl and2-ethyl-10-methyltridecanoic acid; 2,10-diethyl-6-methyl,2-ethyl-6,10-dimethyl, 2-ethyl-6,8-dimethyl, and2-ethyl-4,8-dimethyltetradecanoic acid.

[0021] Yet other substituted fatty acids known in the art include:2,2-diethyl and 6-ethyl-2,4-dimethyldecanoic acid; 4-ethyl-5-methyl and3-ethyl-3-methylundecanoic acid; 2,2-diethyldodecanoic acid;3-ethyl-3-methyltridecanoic acid; 3-ethyl-3-methylpentadecanoic acid;4,6-diethylhexadecanoic acid; 4,6-diethyl and2-ethyl-2-propyloctadecanoic acid; and 3-ethyl-3-methylnonadecanoicacid.

[0022] In referring especially to the early literature, the followingterms have been used as synonyms:

[0023] decanoic acid: capric acid

[0024] undecanoic acid: undecylic acid or hendecanoic acid

[0025] dodecanoic acid: lauric acid

[0026] tridecanoic acid: tridecoic acid

[0027] tetradecanoic acid: myristic acid

[0028] pentadecanoic acid: no early synonym

[0029] hexadecanoic acid: palmitic acid

[0030] heptadecanoic acid: margaric acid

[0031] octadecanoic acid: stearic acid

[0032] nonadecanoic acid: nonadecoic acid

[0033] Additionally, with respect to substitution positions in fattyacids, the following greek letters used in the past are synonymous tothe indicated numbered positions of substitution:

[0034]α=2,β=3,γ=4,δ=5,ε=6,ζ=7,η=8,θ=9,τ=10,κ=11,λ=12,μ=13,ν=14,ξ=15,ο=16,π=17,ρ=18,σ=19.

[0035] Thus, for example, the modern term “2,2-dimethylheptadecanoicacid” and the older term α,α-dimethylmargaric acid” are perfectlysynonymous.

SUMMARY OF THE INVENTION

[0036] The present invention encompasses improvements in consumerproducts, especially laundry detergents and cleaning products, madepossible though innovation in fatty acids and their derivatives.Consumer products ranging from personal care products to cosmetics andpaper products, into which the materials can be formulated, areencompassed.

[0037] More particularly, in one aspect, the invention encompasses acomposition of matter comprising the acid, lower alkyl esters,stereoisomers, or salts of at least one branched carboxylic acidselected from the group consisting of:

[0038] (a) 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 12-, 13-, 14-, 15-16-,17- and 18-methylnonadecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8- and9-methyldecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- and10-methylundecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and11-methyldodecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- and12-methyltridecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-and 13-methyltetradecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13- and 14-methylpentadecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-,8-, 9-, 10-, 11-, 12-, 13-, 14- and 15-methylhexadecanoic acid; 2-, 3-,4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-12-, 13-, 14-, 15- and16-methylheptadecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,12-, 13-, 14-, 15-, 16- and 17-methyloctadecanoic acid; and mixturesthereof;

[0039] (b) 2,5-, 2,7-, and 2,9-dimethyldecanoic acid; 2,5-, 2,7-, 2,9-,and 2,10-dimethylundecanoic acid; 2,5-, 2,7-, 2,9- and2,11-dimethyldodecanoic acid;

[0040] 2,3-, 2,7-, 2,9-, 2,11- and 2,12-dimethyltridecanoic acid; 2,5-,2,7-, 2,9-, 2,11-, 2,12- and 2,13-dimethyltetradecanoic acid; 2,3-,2,5-, 2,7-, 2,8-, 2,9-, 2,11- and 2,13-dimethylpentadecanoic acid; 2,3-,2,5-, 2,7-, 2,8-, 2,9-, 2,11-, 2,13- and 2,15-dimethylhexadecanoic acid;2,3-, 2,7-, 2,8-, 2,9-, 2,11-, 2,12-, 2,13-, 2,14-, 2,15- and2,16-dimethylheptadecanoic acid; 2,5-, 2,6-, 2,7-, 2,8-2,10-, 2,11-,2,12-, 2,13-, 2,14-, 2,15-, 2,16- and 2,17-dimethyloctadecanoic acid;and mixtures thereof;

[0041] (c) 3,4-, 3,5-, 3,6-, 3,8-, 3,9-, 4,5-, 4,7-, 4,9-, 5,6-, 5,7-,5,8-, 6,7-, 6,8-, 6,9-, 7,8-, 7,9- and 8,9-, dimethyldecanoic acid;3,4-, 3,6-, 3,8-, 3,10-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 5,6-, 5,7-,5,8-, 5,9-, 5,10-, 6,7-, 6,8-, 6,9-, 6,10-, 7,8-, 7,9-, 7,10-, 8,9-,8,10- and 9,10-, dimethylundecanoic acid; 3,4-, 3,6-, 3,8-, 3,10-, 4,5-,4,6-, 4,7-, 4,9-, 4,11-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-, 6,7-,6,8-, 6,9-, 6,10-, 6,11-, 7,8-, 7,9-, 7,10-, 7,11-, 8,9-, 8,10-, 8,11-,9,10-, 9,11-, and 10,11-dimethyldodecanoic acid; 3,6-, 3,8-, 3,10-,3,12-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-, 5,6-, 5,8-, 5,9-,5,10-, 5,11-, 5,12-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 7,8-, 7,9-,7,10-, 7,11-, 7,12-, 8,9-, 8,10-, 8,11-, 8,12-, 9,10-, 9,11-, 9,12-,10,11-, 10,12- and 11,12-dimethyltridecanoic acid; 3,4-, 3,6-, 3,8-,3,10-, 3,12-, 3,13-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-, 4,13-,5,6-, 5,8-, 5,10-, 5,11-, 5,12-, 5,13-, 6,7-, 6,8-, 6,9-, 6,11-, 7,9-,7,10-, 7,11-, 7,12-, 7,13-8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 9,10-,9,11-, 9,12-, 10,11-, 10,12-, 11,12-, 11,13- and 12,13-,dimethyltetradecanoic acid; 3,4-, 3,8-, 3,10-, 3,12-, 3,14-, 4,5-, 4,6-,4,7-, 4,9-, 4,11-, 4,12-, 4,13-, 4,14-, 5,6-, 5,7-, 5,8-, 5,10-, 5,11-,5,12-, 5,13-, 5,14-, 6,7-, 6,9-, 6,11-, 6,12-, 6,13-, 6,14-, 7,8-, 7,9-,7,10-, 7,11-, 7,12-, 7,13-, 7,14-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-,8,14-, 9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 10,11-, 10,12-, 10,13-,10,14-, 11,12-, 11,13-, 11,14-, 12,13-, 12,14- and 13,14-,dimethylpentadecanoic acid; 3,4-, 3,5-, 3,6-, 3,8-, 3,9-, 3,10-, 3,11-,3,12-, 3,13-, 3,14-, 3,15-, 4,5-, 4,6-, 4,7-, 4,9-, 4,11-, 4,12-, 4,13-,4,15-, 5,6-, 5,7-, 5,8-, 5,10-, 5,11-, 5,12-, 5,13-, 5,14-, 5,15-, 6,7-,6,8-, 6,9-, 6,10-, 6,11-, 6,13-, 6,14-, 6,15-, 7,8-, 7,10-, 7,11-,7,12-, 7,13-, 7,14, 7,15-, 8,9-, 8,10-, 8,11-, 8,13-, 8,15-, 9,10-,9,11-, 9,12-, 9,13-, 9,14-, 9,15-, 10,11-, 10,12-, 10,13-, 10,14-,10,15-, 11,12-, 11,13-, 11,14-, 12,13-, 12,14-, 12,15-, 13,14-, 13,15-and 14,15-, dimethylhexadecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-,3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 3,14-, 3,15-, 3,16-, 4,5-, 4,6-, 4,7-,4,8-, 4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 4,14-, 4,15-, 4,16-, 5,6-, 5,7-,5,8-, 5,10-, 5,11-, 5,12-, 5,13-, 5,14-, 5,15-, 5,16-, 6,7-, 6,8-, 6,9-,6,10-, 6,11-, 6,12-, 6,13-, 6,14-, 6,15-, 6,16-, 7,8-, 7,9-, 7,10-,7,11-, 7,12-, 7,13-, 7,14-, 7,15-, 7,16-, 8,9-, 8,11-, 8,12-, 8,13-,8,14-, 8,15-, 8,16-, 9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 9,15-, 9,16-,10,11-, 10,12-, 10,13-, 10,14-, 10,15-, 10,16-, 11,12-, 11,13-, 11,14-,11,15-, 11,16-, 12,13-, 12,14-, 12,15-, 13,14-, 13,15-, 13,16-, 14,15-,14,16- and 15,16-, dimethylheptadecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-,3,8-, 3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 3,14-, 3,15-, 3,16-, 3,17-,4,5-, 4,6-, 4,7-, 4,8-, 4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 4,14-, 4,15-,4,16-, 4,17-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-, 5,12-, 5,13-, 5,14-,5,15-, 5,16-, 5,17-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 6,13-,6,14-, 6,15-, 6,16-, 6,17-, 7,8-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-,7,15-, 7,16-, 7,17-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 8,14-, 8,15-,8,16-, 8,17-, 9,12-, 9,13-, 9,14-, 9,15-, 9,16-, 9,17-, 10,11-, 10,12-,10,13-, 10,14-, 10,15-, 10,16-, 10,17-, 11,12-, 11,13-, 11,14-, 11,15-,11,16-, 11,17-, 12,13-, 12,14-, 12,15-, 12,16-, 12,17-, 13,14-, 13,15-,13,16-, 13,17-, 14,15-, 14,16-, 14,17-, 15,16-, 15,17- and16,17-dimethyloctadecanoic acid; and mixtures thereof;

[0042] (d) 3-, 4-, 5-, 6-, 7- and 8-methyl-2-ethylnonanoic acid; 3-, 4-,5-, 7-, 8- and 9-methyl-2-ethyldecanoic acid; 3-, 4-, 5-, 7-, 8-, 9- and10-methyl-2-ethylundecanoic acid; 3-, 4-, 5-, 7-, 8-, 9-, 10- and 11-,methyl-2-ethyldodecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9- and11-methyl-2-ethyltridecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,12- and 13-methyl-2-ethyltetradecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-,10-, 11-, 12-, 13- and 14-methyl-2-ethylpentadecanoic acid; 3-, 4-, 5-,6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14- and15-methyl-2-ethylhexadecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13-, 14-, 15- and 16-methyl-2-ethylheptadecanoic acid; andmixtures thereof;

[0043] (e) 3-, 5-, 6-, 7- and 8-ethyldecanoic acid; 3-, 4-, 5-, 6-, 7-,8- and 9-ethylundecanoic acid; 3-, 5-, 7-, 8- and 9-ethyldodecanoicacid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-ethyltridecanoic acid; 3-,5-, 7-, 8-, 9-, 10-, 11- and 12-ethyltetradecanoic acid; 2-, 3-, 5-, 6-,7-, 8-, 9-, 10-, 11- and 12-ethylpentadecanoic acid; 3-, 4-, 5-, 6-, 7-,8-, 9-, 10-, 11-, 12-, 13- and 14-ethylhexadecanoic acid; 3-, 4-, 5-,6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- and 14-ethylheptadecanoic acid; 4-,5-, 6-, 7-, 8-, 10-, 11-, 13-, 14- and 15-ethyloctadecanoic acid; andmixtures thereof;

[0044] (f) 3-, 4-, 5-, 6- and 7-propyldecanoic acid; 4-, 5-, 6-, 7- and8-propylundecanoic acid; 3-, 4-, 5-, 7-, 8- and 9-propyldodecanoic acid;3-, 4-, 5-, 6-, 7-, 8-, 9- and 10-propyltridecanoic acid; 4-, 5-, 6-,7-, 8-, 9-, 10- and 11-propyltetradecanoic acid; 4-, 5-, 6-, 7-, 8-, 9-,10-, 11- and 12-propylpentadecanoic acid; 5-, 6-, 7-, 8-, 9-, 10-, 11-,12- and 13-propylhexadecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13- and 14-propylheptadecanoic acid; and mixtures thereof;

[0045] (g) 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 4,6-, 4,7-, 5,6-, 5,7- and6,7-dimethyl-2-ethyloctanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-,4,6-, 4,7-, 4,8-, 5,6-, 5,7-, 5,8-, 6,7-, 6,8- and 7,8-,dimethyl-2-ethylnonanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 4,5-,4,6-, 4,7-, 4,8-, 4,9-, 5,6-, 5,7-, 5,8-, 5,9-, 6,7-, 6,8-, 6,9-, 7,8-,7,9- and 8,9-dimethyl-2-ethyldecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-,3,8-, 3,9-, 3,10-, 4,5-, 4,7-, 4,8-, 4,9-, 4,10-, 5,6-, 5,7-, 5,8-,5,9-, 5,10-, 6,7-, 6,9-, 6,10-, 7,8-, 7,9-, 7,10-, 8,9-, 8,10- and9,10-, dimethyl-2-ethylundecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-,3,9-, 3,10-, 3,11-, 4,5-, 4,7-, 4,8-, 4,9-, 4,10-, 4,11-, 5,6-, 5,7-,5,8-, 5,9-, 5,10-, 5,11-, 6,7-, 6,9-, 6,11-, 7,8-, 7,9-, 7,10-, 7,11-,8,9-, 8,10-, 8,11-, 9,10-, 9,11- and 10,11-dimethyl-2-ethyldodecanoicacid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-, 4,5-,4,6-, 4,7-, 4,8-, 4,9-, 4,10-, 4,11-, 4,12-, 5,6-, 5,7-, 5,8-, 5,9-,5,10-, 5,11-, 5,12-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 7,8-, 7,9-,7,10-, 7,11-, 7,12-, 8,9-, 8,10-, 8,11-, 8,12-, 9,10-, 9,11-, 9,12-,10,11-, 10,12- and 11,12-dimethyl-2-ethyltridecanoic acid; 3,4-, 3,5-,3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 4,5-, 4,6-, 4,7-,4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-,5,12-, 5,13-, 6,7-, 6,9-, 6,11-, 6,12-, 6,13-, 7,8-, 7,9-, 7,10-, 7,11-,7,12-, 7,13-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 9,10-, 9,11-, 9,12-,9,13-, 10,11-, 10,12-, 10,13-, 11,12-, 11,13- and12,13-dimethyl-2-ethyltetradecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-,3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 3,14-, 4,5-, 4,6-, 4,7-, 4,8-, 4,9-,4,10-, 4,11-, 4,12-, 4,13-, 4,14-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-,5,12-, 5,13-, 5,14-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 6,13-,6,14-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-, 8,9-, 8,10-,8,11-, 8,12-, 8,13-, 8,14-, 9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 10,11-,10,12-, 10,13-, 10,14-, 11,12-, 11,13-, 11,14-, 12,13-, 12,14- and13,14-dimethyl-2-ethylpentadecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-,3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 3,14-, 3,15-, 4,5-, 4,6-, 4,7-, 4,8-,4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 4,14-, 4,15-, 5,6-, 5,7-, 5,8-, 5,9-,5,10-, 5,11-, 5,12-, 5,13-, 5,14-, 5,15-, 6,7-, 6,8-, 6,9-, 6,10-,6,11-, 6,12-, 6,13-, 6,14-, 6,15-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-,7,13-, 7,14-, 7,15-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 8,14-, 8,15-,9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 9,15-, 10,11-, 10,12-, 10,13-,10,14-, 10,15-, 11,12-, 11,13-, 11,14-, 11,15-, 12,13-, 12,14-, 12,15-,13,14-, 13,15- and 14,15-dimethyl-2-ethylhexadecanoic acid; and mixturesthereof;

[0046] (h) 3-, 4-, 5- and 6-, methyl-2-propylheptanoic acid; 3-, 4-, 5-,6- and 7-methyl-2-propyloctanoic acid; 3-, 4-, 5-, 6-, 7- and8-methyl-2-propylnonanoic acid; 3-, 4-, 5-, 6-, 7-, 8- and9-methyl-2-propyldecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9- and10-methyl-2-propylundecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and11-methyl-2-propyldodecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-and 12-methyl-2-propyltridecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-,11-, 12- and 13-methyl-2-propyltetradecanoic acid; 3-, 4-, 5-, 6-, 7-,8-, 9-, 10-, 11-, 12-, 13- and 14-methyl-2-propylpentadecanoic acid; andmixtures thereof;

[0047] (i) 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-,2,3,11-, 2,3,12-, 2,3,13-, 2,3,14-, 2,3,15-, 2,3,16-, 2,4,5-, 2,4,6-,2,4,7-, 2,4,8-, 2,4,9-, 2,4,10-, 2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-,2,4,15-, 2,4,16-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-,2,5,12-, 2,5,13-, 2,5,14-, 2,5,15-, 2,5,16-, 2,6,7-, 2,6,8-, 2,6,9-,2,6,10-, 2,6,11-, 2,6,12-, 2,6,13-, 2,6,14-, 2,6,15-, 2,6,16-, 2,7,8-,2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-, 2,7,15-, 2,7,16-,2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,8,13-, 2,8,14-, 2,8,15-, 2,8,16-,2,9,10-, 2,9,11-, 2,9,12-, 2,9,13-, 2,9,14-, 2,9,15-, 2,9,16-, 2,10,11-,2,10,12-, 2,10,13-, 2,10,14-, 2,10,15-, 2,10,16-, 2,11,12-, 2,11,13-,2,11,14-, 2,11,15-, 2,11,16-, 2,12,13-, 2,12,14-, 2,12,15-, 2,12,16-,2,13,14-, 2,13,15-, 2,13,16-, 2,14,15-, 2,14,16-, 2,15,16-, 3,4,5-,3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-,3,4,14-, 3,4,15-, 3,4,16-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-, 3,5,10-,3,5,11-, 3,5,12-, 3,5,13-, 3,5,14-, 3,5,15-, 3,5,16-, 3,6,7-, 3,6,8-,3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,6,13-, 3,6,14-, 3,6,15-, 3,6,16-,3,7,8-, 3,7,9-, 3,7,10-, 3,7,11-, 3,7,12-, 3,7,13-, 3,7,14-, 3,7,15-,3,7,16-, 3,8,9-, 3,8,10-, 3,8,11-, 3,8,12-, 3,8,13-, 3,8,15-, 3,8,14-,3,8,16-, 3,9,10-, 3,9,11-, 3,9,12-, 3,9,13-, 3,9,14-, 3,9,15-, 3,9,16-,3,10,11-, 3,10,12-, 3,10,13-, 3,10,14-, 3,10,15-, 3,10,16-, 3,11,12-,3,11,14-, 3,11,13-, 3,11,15-, 3,11,16-, 3,12,13-, 3,12,14-, 3,12,15-,3,12,16-, 3,13,14-, 3,13,15-, 3,13,16-, 3,14,15-, 3,14,16-, 3,15,16-,4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-, 4,5,13-,4,5,14-, 4,5,15-, 4,5,16-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-,4,6,12-, 4,6,13-, 4,6,14-, 4,6,15-, 4,6,16-, 4,7,8-, 4,7,9-, 4,7,10-,4,7,11-, 4,7,12-, 4,7,13-, 4,7,14-, 4,7,15-, 4,7,16-, 4,8,9-, 4,8,10-,4,8,11-, 4,8,13-, 4,8,14-, 4,8,15-, 4,8,16-, 4,9,10-, 4,9,11-, 4,9,12-,4,9,13-, 4,9,14-, 4,9,15-, 4,9,16-, 4,10,11-, 4,10,12-, 4,10,13-,4,10,14-, 4,10,15-, 4,10,16-, 4,11,12-, 4,11,13-, 4,11,14-, 4,11,15-,4,11,16-, 4,12,13, 4,12,14-, 4,12,15-, 4,12,16-, 4,13,14-, 4,13,15-,4,13,16-, 4,14,15-, 4,14,16-, 4,15,16-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-,5,6,11-, 5,6,12-, 5,6,13-, 5,6,14-, 5,6,15-, 5,6,16-, 5,7,8-, 5,7,9-,5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-, 5,7,14-, 5,7,15-, 5,7,16-, 5,8,9-,5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-, 5,8,14-, 5,8,15-, 5,8,16-, 5,9,10-,5,9,11-, 5,9,12-, 5,9,13-, 5,9,14-, 5,9,15-, 5,9,16-, 5,10,11-,5,10,12-, 5,10,13-, 5,10,14-, 5,10,15-, 5,10,16-, 5,11,12-, 5,11,13-,5,11,14-, 5,11,15-, 5,12,13-, 5,12,14-, 5,12,15-, 5,12,16-, 5,13,14-,5,13,15-, 5,13,16-, 5,14,15-, 5,14,16-, 5,15,16-, 6,7,8-, 6,7,9-,6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-, 6,7,15-, 6,7,16-, 6,8,9-,6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,8,15-, 6,8,16-, 6,9,10-,6,9,11-, 6,9,12-, 6,9,13-, 6,9,14-, 6,9,15-, 6,9,16-, 6,10,11-,6,10,12-, 6,10,13-, 6,10,14-, 6,10,15-, 6,10,16-, 6,11,12-, 6,11,13-,6,11,14-, 6,11,15-, 6,11,16-, 6,12,13-, 6,12,14-, 6,12,15-, 6,12,16-,6,13,14-, 6,13,15-, 6,13,16-, 6,14,15-, 6,14,16-, 6,15,16-, 7,8,9-,7,8,10-, 7,8,11-, 7,8,12-, 7,8,13-, 7,8,14-, 7,8,15-, 7,8,16-, 7,9,10-,7,9,11-, 7,9,12-, 7,9,13-, 7,9,14-, 7,9,15-, 7,9,16-, 7,10,11-,7,10,12-, 7,10,13-, 7,10,14-, 7,10,15-, 7,10,16-, 7,11,12-, 7,11,13-,7,11,14-, 7,11,15-, 7,11,16-, 7,12,13-, 7,12,14-, 7,12,15-, 7,12,16-,7,13,14-, 7,13,15-, 7,13,16-, 7,14,15-, 7,14,16-, 7,15,16-, 8,9,10-,8,9,11-, 8,9,12-, 8,9,13-, 8,9,14-, 8,9,15-, 8,9,16-, 8,10,11-,8,10,12-, 8,10,13-, 8,10,14-, 8,10,15-, 8,10,16-, 8,11,12-, 8,11,13-,8,11,14-, 8,11,15-, 8,11,16-, 8,12,13-, 8,12,14-, 8,12,15-, 8,12,16-,8,13,14-, 8,13,15-, 8,13,16-, 8,14,15-, 8,14,16-, 8,15,16-, 9,10,11-,9,10,12-, 9,10,13-, 9,10,14-, 9,10,15-, 9,10,16-, 9,11,12-, 9,11,13-,9,11,14-, 9,11,15-, 9,11,16-, 9,12,13-, 9,12,14-, 9,12,15-, 9,12,16-,9,13,14-, 9,13,15-, 9,13,16-, 9,14,15-, 9,14,16-, 9,15,16-, 10,11,12-,10,11,13-, 10,11,14-, 10,11,15-, 10,11,16-, 10,12,13-, 10,12,14-,10,12,15-, 10,12,16-, 10,13,14-, 10,13,15-, 10,13,16-, 10,14,15-,10,14,16-, 10,15,16-, 11,12,13-, 11,12,14-, 11,12,15-, 11,12,16-,11,13,14-, 11,13,15-, 11,13,16-, 11,14,15-, 11,14,16-, 11,15,16-,12,13,14-, 12,13,15-, 12,13,16-, 12,14,15-, 12,14,16-, 12,15,16-,13,14,15-13,14,16-, 13,15,16- and 14,15,16-trimethylheptadecanoic acid;2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,3,12-,2,3,13-, 2,3,14-, 2,3,15-, 2,4,5-, 2,4,6-, 2,4,7-, 2,4,9-, 2,4,10-,2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-, 2,4,15-, 2,5,6-, 2,5,7-, 2,5,8-,2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-, 2,5,13-, 2,5,14-, 2,5,15-, 2,6,7-,2,6,8-, 2,6,9-, 2,6,10-, 2,6,11-, 2,6,12-, 2,6,13-, 2,6,14-, 2,6,15-,2,7,8-, 2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-, 2,7,15-,2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,8,13-, 2,8,14-, 2,8,15-, 2,9,10-,2,9,11-, 2,9,12-, 2,9,13-, 2,9,14-, 2,9,15-, 2,10,11-, 2,10,12-,2,10,13-, 2,10,14-, 2,10,15-, 2,11,12-, 2,11,13-, 2,11,14-, 2,11,15-,2,12,13-, 2,12,14-, 2,12,15-, 2,13,14-, 2,13,15-, 2,14,15-, 3,4,5-,3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-,3,4,14-, 3,4,15-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-, 3,5,10-, 3,5,11-,3,5,12-, 3,5,13-, 3,5,14-, 3,5,15-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-,3,6,11-, 3,6,12-, 3,6,13-, 3,6,14-, 3,6,15-, 3,7,8-, 3,7,9-, 3,7,10-,3,7,11-, 3,7,12-, 3,7,13-, 3,7,14-, 3,7,15-, 3,8,9-, 3,8,10-, 3,8,11-,3,8,12-, 3,8,13-, 3,8,14-, 3,8,15-, 3,9,10-, 3,9,11-, 3,9,12-, 3,9,13-,3,10,11-, 3,10,12-, 3,10,13-, 3,10,14-, 3,10,15-, 3,11,12-, 3,11,13-,3,11,14-, 3,11,15-, 3,12,13-, 3,12,14-, 3,12,15-, 3,13,14-, 3,13,15-,3,14,15-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-,4,5,13-, 4,5,14-, 4,5,15-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-,4,6,12-, 4,6,13-, 4,6,14-, 4,6,15-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-,4,7,12-, 4,7,13-, 4,7,14-, 4,7,15-, 4,8,9-, 4,8,10-, 4,8,11-, 4,8,12-,4,8,13-, 4,8,14-, 4,8,15-, 4,9,10-, 4,9,11-, 4,9,12-, 4,9,13-, 4,9,14-,4,9,15-, 4,10,11-, 4,10,12-, 4,10,13-, 4,10,14-, 4,10,15-, 4,11,12-,4,11,13-, 4,11,14-, 4,11,15-, 4,12,13-, 4,12,14-, 4,12,15-, 4,13,14-,4,13,15-, 4,14,15-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-,5,6,13-, 5,6,14-, 5,6,15-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-,5,7,13-, 5,7,14-, 5,7,15-, 5,8,9-5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-,5,8,14-, 5,8,15-, 5,9,10-, 5,9,11-5,9,12-, 5,9,13-, 5,9,14-, 5,9,15-,5,10,11-, 5,10,12-, 5,10,13-, 5,10,14-, 5,10,15-, 5,11,12-, 5,11,13-,5,11,14-, 5,11,15-, 5,12,13-, 5,12,14-, 5,12,15-, 5,13,14-, 5,13,15-,5,14,15-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-,6,7,15-, 6,8,9-6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,8,15-,6,9,10-, 6,9,11-, 6,9,12-, 6,9,13-, 6,9,14-, 6,9,15-, 6,10,11-,6,10,12-, 6,10,13-, 6,10,14-, 6,10,15-, 6,11,12-, 6,11,13-, 6,11,14-,6,11,15-, 6,12,13-, 6,12,14-, 6,12,15-, 6,13,14-, 6,13,15-, 6,14,15-,7,8,9-, 7,8,10-, 7,8,11-, 7,8,12-, 7,8,13-, 7,8,14-, 7,8,15-, 7,9,10-,7,9,11-, 7,9,12-, 7,9,13-, 7,9,14-, 7,9,15-, 7,10,11-, 7,10,12-,7,10,13-, 7,10,14-, 7,10,15-, 7,11,12-, 7,11,13-, 7,11,14-, 7,11,15-,7,12,13-, 7,12,14-, 7,12,15-, 7,13,14-, 7,13,15-, 7,14,15-, 8,9,10-,8,9,11-, 8,9,12-, 8,9,13-, 8,9,14-, 8,9,15-, 8,10,11-, 8,10,12-,8,10,13-, 8,10,14-, 8,10,15-, 8,11,12-, 8,11,13-, 8,11,14-, 8,11,15-,8,12,13-, 8,12,14-, 8,12,15-, 8,13,14-, 8,13,15-, 8,14,15-, 9,10,11-,9,10,12-, 9,10,13-, 9,10,14-, 9,10,15-, 9,11,12-, 9,11,13-, 9,11,14-,9,11,15-, 9,12,13-, 9,12,14-, 9,12,15-, 9,13,14-, 9,13,15-, 9,14,15-,10,11,12-, 10,11,13-, 10,11,14-, 10,11,15-, 10,12,13-, 10,12,14-,10,12,15-, 10,13,14-, 10,13,15-, 10,14,15-, 11,12,13-, 11,12,14-,11,12,15-, 11,13,14-, 11,13,15-, 11,14,15-, 12,13,14-, 12,13,15-,12,14,15- and 4,15-trimethylhexadecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-,2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,3,12-, 2,3,13-, 2,3,14-,2,4,5-, 2,4,7-, 2,4,9-, 2,4,10-, 2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-,2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-, 2,5,13-,2,5,14-, 2,6,7-, 2,6,8-, 2,6,9-, 2,6,10-, 2,6,11-, 2,6,12-, 2,6,13-,2,6,14-, 2,7,8-, 2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-,2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,8,13-, 2,8,14-, 2,9,10-, 2,9,11-,2,9,12-, 2,9,13-, 2,9,14-, 2,10,11-, 2,10,12-, 2,10,13-, 2,10,14-,2,11,12-, 2,11,13-, 2,11,14-, 2,12,13-, 2,12,14-, 2,13,14-, 3,4,5-,3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-,3,4,14-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,10-, 3,5,11-, 3,5,12-, 3,5,13-,3,5,14-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,6,13-,3,6,14-, 3,7,8-, 3,7,10-, 3,7,12-, 3,7,13-, 3,7,14-, 3,8,9-, 3,8,10-,3,8,11-, 3,8,12-, 3,8,13-, 3,8,14-, 3,9,10-, 3,9,12-, 3,9,13-, 3,9,14-,3,10,11-, 3,10,12-, 3,10,13-, 3,10,14-, 3,11,12-, 3,11,13-, 3,11,14-,3,12,13-, 3,12,14-, 3,13,14-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-,4,5,11-, 4,5,12-, 4,5,13-, 4,5,14-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-,4,6,11-, 4,6,12-, 4,6,13-, 4,6,14-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-,4,7,12-, 4,7,13-, 4,7,14-, 4,8,9-, 4,8,10-, 4,8,11-, 4,8,12-, 4,8,13-,4,8,14-, 4,9,10-, 4,9,11-, 4,9,12-, 4,9,13-, 4,9,14-, 4,10,11-,4,10,12-, 4,10,13-, 4,10,14-, 4,11,12-, 4,11,13-, 4,11,14-, 4,12,13-,4,12,14-, 4,13,14-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-,5,6,13-, 5,6,14-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-,5,7,14-, 5,8,9-, 5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-, 5,8,14-, 5,9,10-,5,9,11-, 5,9,12-, 5,9,13-, 5,9,14-, 5,10,11-, 5,10,12-, 5,10,13-,5,10,14-, 5,11,12-, 5,11,13-, 5,11,14-, 5,12,13-, 5,12,14-, 5,13,14-,6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-, 6,8,9-,6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,9,10-, 6,9,11-, 6,9,12-,6,9,13-, 6,9,14-, 6,10,11-, 6,10,12-, 6,10,13-, 6,11,12-, 6,11,13-,6,11,14-, 6,12,13-, 6,12,14-, 6,13,14-, 7,8,9-, 7,8,10-, 7,8,11-,7,8,12-, 7,8,13-, 7,8,14-, 7,9,10-, 7,9,11-, 7,9,12-, 7,9,13-, 7,9,14-,7,10,11-, 7,10,12-, 7,10,13-, 7,10,14-, 7,11,12-, 7,11,13-, 7,11,14-,7,12,13-, 7,12,14-, 7,13,14-, 8,9,10-, 8,9,11-, 8,9,12-, 8,9,13-,8,9,14-, 8,10,11-, 8,10,12-, 8,10,13-, 8,10,14-, 8,11,12-, 8,11,13-,8,11,14-, 8,12,13-, 8,12,14-, 8,13,14-, 9,10,11-, 9,10,12-, 9,10,13-,9,10,14-, 9,11,12-, 9,11,13-, 9,11,14-, 9,12,13-, 9,12,14-, 9,13,14-,10,11,12-, 10,11,13-, 10,11,14-, 10,12,13-, 10,12,14-, 10,13,14-,11,12,13-, 11,12,14-, 11,13,14- and 12,13,14-trimethylpentadecanoicacid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-,2,3,12-, 2,3,13-, 2,4,5-, 2,4,7-, 2,4,9-, 2,4,10-, 2,4,11-, 2,4,12-,2,4,13-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-,2,5,13-, 2,6,7-, 2,6,8-, 2,6,9-, 2,6,11-, 2,6,12-, 2,6,13-, 2,7,8-,2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,8,9-, 2,8,10-, 2,8,11-,2,8,12-, 2,8,13-, 2,9,10-, 2,9,11-, 2,9,12-, 2,9,13-, 2,10,11-,2,10,12-, 2,10,13-, 2,11,12-, 2,11,13-, 2,12,13-, 3,4,5-, 3,4,6-,3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-, 3,5,6-,3,5,7-, 3,5,8-, 3,5,9-, 3,5,10-, 3,5,11-, 3,5,12-, 3,5,13-, 3,6,7-,3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,7,8-, 3,7,10-, 3,7,11-,3,7,12-, 3,7,13-, 3,8,9-, 3,8,10-, 3,8,11-, 3,8,12-, 3,8,13-, 3,9,10-,3,9,11-, 3,9,12-, 3,9,13-, 3,10,11-, 3,10,12-, 3,10,13-, 3,11,12-,3,11,13-, 3,12,13-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-,4,5,12-, 4,5,13-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-, 4,6,12-,4,6,13-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-, 4,7,12-, 4,7,13-, 4,8,9-,4,8,10-, 4,8,11-, 4,8,12-, 4,8,13-, 4,9,10-, 4,9,11-, 4,9,12-, 4,9,13-,4,10,11-, 4,10,12-, 4,10,13-, 4,11,12-, 4,11,13-, 4,12,13-, 5,6,7-,5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-, 5,6,13-, 5,7,8-, 5,7,9-,5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-, 5,8,9-, 5,8,10-, 5,8,11-, 5,8,12-,5,8,13-, 5,9,10-, 5,9,11-, 5,9,12-, 5,10,11-, 5,10,12-, 5,10,13-,5,11,12-, 5,11,13-, 5,12,13-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-,6,7,13-, 6,8,9-, 6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,9,10-, 6,9,11-,6,9,12-, 6,9,13-, 6,10,11-, 6,10,12-, 6,10,13-, 6,11,12-, 6,11,13-,6,12,13-, 7,8,9-, 7,8,10-, 7,8,11-, 7,8,12-, 7,8,13-, 7,9,10-, 7,9,11-,7,9,12-, 7,9,13-, 7,10,11-, 7,10,12-, 7,10,13-, 7,11,12-, 7,11,13-,7,12,13-, 8,9,10-, 8,9,11-, 8,9,12-, 8,9,13-, 8,10,11-, 8,10,12-,8,10,13-, 8,11,12-, 8,11,13-, 8,12,13-, 9,10,11-, 9,10,12-, 9,10,13-,9,11,12-, 9,11,13-, 9,12,13-, 10,11,12-, 10,11,13-, 10,12,13- and11,12,13-trimethyltetradecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-,2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,3,12-, 2,4,5-, 2,4,7-, 2,4,9-,2,4,11-, 2,4,12-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-,2,5,12-, 2,6,7-, 2,6,8-, 2,6,9-, 2,6,11-, 2,6,12-, 2,7,8-, 2,7,9-,2,7,10-, 2,7,11-, 2,7,12-, 2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,9,10-,2,9,11-, 2,9,12-, 2,10,11-, 2,10,12-, 2,11,12-, 3,4,5-, 3,4,6-, 3,4,7-,3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,5,6-, 3,5,7-, 3,5,8-,3,5,10-, 3,5,11-, 3,5,12-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-,3,6,12-, 3,7,8-, 3,7,10-, 3,7,11-, 3,7,12-, 3,8,9-, 3,8,10-, 3,8,11-,3,8,12-, 3,9,10-, 3,9,11-, 3,9,12-, 3,10,11-, 3,10,12-, 3,11,12-,4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-, 4,6,7-,4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-, 4,6,12-, 4,7,8-, 4,7,9-, 4,7,10-,4,7,11-, 4,7,12-, 4,8,9-, 4,8,10-, 4,8,11-, 4,9,10-, 4,9,11-, 4,9,12-,4,10,11-, 4,10,12-, 4,11,12-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-,5,6,12-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-, 5,8,9-, 5,8,10-,5,8,11-, 5,8,12-, 5,9,10-, 5,9,11-, 5,9,12-, 5,10,11-, 5,10,12-,5,11,12-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-, 6,8,9-, 6,8,10-,6,8,11-, 6,8,12-, 6,9,10-, 6,9,11-, 6,9,12-, 6,10,11-, 6,10,12-,6,11,12-, 7,8,9-, 7,8,10-, 7,8,11-, 7,8,12-, 7,9,10-, 7,9,11-, 7,9,12-,7,10,11-, 7,10,12-, 7,11,12-, 8,9,10-, 8,9,11-, 8,9,12-, 8,10,11-,8,10,12-, 8,11,12-, 9,10,11-, 9,10,12-, 9,11,12- and10,11,12-trimethyltridecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-,2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,4,5-, 2,4,7-, 2,4,9-, 2,4,10-,2,4,11-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,6,7-,2,6,8-, 2,6,9-, 2,6,11-, 2,7,8-, 2,7,9-, 2,7,10-, 2,7,11-, 2,8,9-,2,8,10-, 2,8,11-, 2,9,10-, 2,9,11-, 2,10,11-, 3,4,5-, 3,4,6-, 3,4,7-,3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-,3,5,10-, 3,5,11-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,7,8-,3,7,9-, 3,7,10-, 3,8,9-, 3,8,10-, 3,8,11-, 3,9,10-, 3,9,11-, 3,10,11-,4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,6,7-, 4,6,8-,4,6,9-, 4,6,10-, 4,6,11-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-, 4,8,9-,4,8,10-, 4,8,11-, 4,9,10-, 4,9,11-, 4,10,11-, 5,6,7-, 5,6,8-, 5,6,9-,5,6,10-, 5,6,11-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,8,9-, 5,8,10-,5,8,11-, 5,9,10-, 5,9,11-, 5,10,11-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-,6,8,9-, 6,8,10-, 6,8,11-, 6,9,10-, 6,9,11-, 6,10,11-, 7,8,9-, 7,8,10-,7,8,11-, 7,9,10-, 7,9,11-, 7,10,11-, 8,9,10-, 8,9,11-, 8,10,11- and9,10,11-trimethyldodecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-,2,3,8-, 2,3,9-, 2,3,10-, 2,4,7-, 2,4,9-, 2,4,10-, 2,5,6-, 2,5,7-,2,5,8-, 2,5,9-, 2,5,10-, 2,6,7-, 2,6,9-, 2,7,8-, 2,7,9-, 2,7,10-,2,8,9-, 2,8,10-, 2,9,10-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-,3,4,10-, 3,5,6-, 3,5,8-, 3,5,9-, 3,5,10-, 3,6,7-, 3,6,8-, 3,6,9-,3,6,10-, 3,7,8-, 3,7,9-, 3,7,10-, 3,8,9-, 3,8,10-, 3,9,10-, 4,5,6-,4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-,4,7,8-, 4,7,9-, 4,7,10-, 4,8,9-, 4,8,10-, 4,9,10-, 5,6,7-, 5,6,8-,5,6,9-, 5,6,10-, 5,7,8-, 5,7,9-, 5,7,10-, 5,8,9-, 5,8,10-, 5,9,10-,6,7,8-, 6,7,9-, 6,7,10-, 6,8,9-, 6,8,10-, 6,9,10-, 7,8,9-, 7,8,10-,7,9,10- and 8,9,10-trimethylundecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-,2,3,7-, 2,3,8-, 2,3,9-, 2,4,5-, 2,4,7-, 2,4,9-, 2,5,6-, 2,5,7-, 2,5,8-,2,6,7-, 2,6,9-, 2,7,8-, 2,7,9-, 2,8,9-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-,3,4,9-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-, 3,6,7-, 3,6,8-, 3,6,9-, 3,7,8-,3,7,9-, 3,8,9-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,6,7-, 4,6,9-, 4,7,8-,4,7,9-, 4,8,9-, 5,6,7-, 5,6,8-, 5,6,9-, 5,7,8-, 5,7,9-, 5,8,9-, 6,7,8-,6,7,9-, 6,8,9- and 7,8,9-trimethyldecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-,2,3,7-, 2,3,8-, 2,4,5-, 2,4,6-, 2,4,7-, 2,4,8-, 2,5,6-, 2,5,7-, 2,5,8-,2,6,7-, 2,6,8-, 2,7,8-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-, 3,5,6-, 3,5,7-,3,5,8-, 3,6,7-, 3,6,8-, 3,7,8-, 4,5,6-, 4,5,7-, 4,5,8-, 4,6,7-, 4,6,8-,4,7,8-, 5,6,7-, 5,6,8-, 5,7,8- and 6,7,8-trimethylnonanoic acid; andmixtures thereof;

[0048] (j) 3-butyl-4-ethyl, 3-pentyl-4-propyl, 3-butyl-4-propyl and3-pentyl-4-ethylheptanoic acid; 3-butyl-4-methyl, 4-propyl-5-ethyl,5-ethyl-6-propyl, 3-pentyl-4-ethyl, 4-butyl-5-propyl, 3-hexyl-4-propyl,3-pentyl-4-methyl, 3-butyl-4-ethyl, 4-butyl-5-ethyl, 4,5-dipropyl,3-pentyl-4-propyl, 3-hexyl-4-ethyl, 3-hexyl-4-butyl and3-heptyl-4-propyloctanoic acid; 4-propyl-5-methyl, 3-pentyl-4-methyl,4-butyl-5-ethyl, 5,6,dipropyl, 3-hexyl-4-ethyl, 4-pentyl-5-propyl,3-heptyl-4-propyl, 3-butyl-4-methyl, 4-butyl-5-methyl, 4-propyl-5-ethyl,5-ethyl-6-propyl, 5-propyl-6-ethyl, 3-hexyl-4-methyl, 3-pentyl-4-ethyl,4-pentyl-5-ethyl, 4-butyl-5-propyl, 3-hexyl-4-propyl, 4-pentyl-5-butyland 4-hexyl-5-propylnonanoic acid; 5-ethyl-6-methyl, 6-methyl-7-ethyl,4-butyl-5-methyl, 4-pentyl-5-ethyl, 5-butyl-6-propyl, 4-propyl-5-methyl,5,6-diethyl, 6,7-diethyl, 3-pentyl-4-methyl, 4-pentyl-5-methyl,6-ethyl-7-propyl, 5-propyl-6-ethyl, 3-hexyl-4-methyl, 3-heptyl-4-ethyl,4-hexyl-5-propyl, 4-butyl-5-ethyl, 6-methyl-7-propyl, 5-propyl-6-methyl,5-butyl-6-ethyl, 3-heptyl-4-methyl, 3-hexyl-4-ethyl, 4-hexyl-5-ethyl,4-pentyl-5-propyl, 5,6-dibutyl, 5-pentyl-6-propyl and3-heptyl-4-methyldecanoic acid; 5-propyl-6-methyl, 6,7-diethyl,7-methyl-8-propyl, 4-pentyl-5-methyl, 5-butyl-6-ethyl, 6,7-dipropyl,3-heptyl-4-methyl, 4-hexyl-5-ethyl, 5-pentyl-6-propyl, 6-methyl-7-ethyl,6-ethyl-7-methyl, 5-ethyl-6-methyl, 7-methyl-8-ethyl, 5-butyl-6-methyl,4-butyl-5-methyl, 6-ethyl-7-propyl, 6-propyl-7-ethyl, 3-hexyl-4-methyl,4-hexyl-5-methyl, 4-pentyl-5-ethyl, 5-pentyl-6-ethyl, 6-propyl-7-butyland 6-butyl-7-propylundecanoic acid; 5-pentyl-6-methyl, 6,7-diethyl,7,8-diethyl, 6-ethyl-7-methyl, 7-methyl-8-ethyl, 5-butyl-6-methyl,7-ethyl-8-propyl, 6-propyl-7-ethyl, 4-hexyl-5-methyl, 5-pentyl-6-ethyl,7-methyl-8-propyl, 6-propyl-7-methyl, 4-pentyl-5-methyl,7-ethyl-8-butyl, 6-butyl-7-ethyl, 6-butyl-7-ethyl, 5-butyl-6-ethyl,6,7-dipropyl and 7,8-dipropyldodecanoic acid; 7-ethyl-8-propyl,7-propyl-8-ethyl, 7,8-dipropyl, 7,8-diethyl, 8-methyl-9-propyl,6-propyl-7-methyl, 5-pentyl-6-methyl, 7-methyl-8-ethyl,6-ethyl-7-methyl, 8-methyl-8-ethyl, 8-methyl-9-butyl, 6-butyl-7-methyl,6-butyl-7-methyl, 5-butyl-6-methyl, 6-propyl-7-ethyl and8-ethyl-9-propyltridecanoic acid; 6-propyl-7-methyl, 9-methyl-10-propyl,8-ethyl-9-propyl, 7-ethyl-8-methyl, 7-propyl-8-ethyl, 8-methyl-9-ethyl,8-methyl-9-propyl, 7-propyl-8-methyl, 7,8-diethyl and8,9-diethyltetradecanoic acid; 8,9-diethyl, 9-methyl-10-propyl,7-propyl-8-methyl, 8-methyl-9-ethyl, 8-ethyl-9-methyl, 7-ethyl-8-methyland 9-methyl-10-ethylpentadecanoic acid; 8-ethyl-9-methyl and9-methyl-10-ethylhexadecanoic acid; and mixtures thereof;

[0049] (k) mixtures of (a) to (j);

[0050] This composition of matter, when added to consumer productformulations, have many valuable effects and uses including, forexample, as surfactants, cosurfactants, foam boosters, suds suppressors,calcium sequestrants/limesoap dispersants, crystal growth modifiers forthe calcium soaps of straight-chain fatty acids, as consumer productphysical property modifiers (for example as viscosity modifiers forliquid detergents), as soil modifiers for improving the removability ofsoil from a substrate, as dual-functional cleaning/care materials, asfungicides or antimicrobials, as consumer product dissolution aids, andas skin or hair feel improvement agents. Other uses, depending on thespecific compounds used, include fabric softening and paper productformulation.

[0051] In a second embodiment of the invention, the branched carboxylicacid in the composition of matter can form one or more ester or amidelinkages with a compound containing a nitrogen, preferably quaternarynitrogen, atom to produce fabric softening actives. Specifically, theactives preferably have the formulas:

[(R)_(4−m)−N(+)−[(CH₂)_(n)−Y−R¹]_(m)]X⁽⁻⁾  1)

[0052] wherein each R substituent is hydrogen or a short chain C₁-C₆,preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, ormixtures thereof; each m is 2 or 3, preferably 2; each n is from 1 toabout 4, preferably 2; each Y is —O—(O)C— or —(R)N—(O)C— preferably—O—(O)C—; the sum of carbons in each R¹, plus one when Y is —O—(O)C— or—(R)N—(O)C— (“YR¹ sum”), is C₆-C₂₂, preferably C₁₂₋₂₂, more preferablyC₁₄-C₂₀, (hereinafter, R¹ and YR¹ are used interchangeably to representthe hydrophobic chain, the R¹ chain lengths in general being evennumbered for fatty alcohols and odd for fatty acids), but no more thanone YR¹ sum being less than about 12 and then the other R¹, or YR¹, sumis at least about 16, with each R¹ comprising a long chain C₅-C₂₁ (orC₆-C₂₂), preferably C₁₀-C₂₀ (or C₉-C₁₉) unsaturated alkyl, mostpreferably C₁₂-C 1₈ (or C₁₁-C₁₇) unsaturated alkyl, or at lest one ofthe branched carboxylic acid in the composition of matter the ratio ofthe branched carboxylic acid to unsaturated alkyl being from about 1:0to about 5:95, preferably from about 75:25 to about 25:75, morepreferably from about 50:50 to about 30:70, and for the unsaturatedalkyl group, the Iodine Value of the parent fatty acid of this R¹ groupis preferably from about 20 to about 140, more preferably from about 50to about 130; and most preferably from about 70 to about 115 and whereinthe counterion, X—, can be any softener-compatible anion, preferably,chloride, bromide, methylsulfate, ethylsulfate, sulfate, and/or nitrate,more preferably chloride and/or methylsulfate;

[0053] wherein each Y, R, R¹, and X⁽⁻⁾ have the same meanings as before(Such compounds include those having the formula:

[CH₃]₃ N(+)[CH₂CH(CH₂O(O)CR¹)O(O)CR¹]Cl⁽⁻⁾

[0054] where —O—(O)CR¹ is derived partly from unsaturated, e.g., oleic,fatty acid and, preferably, each R is a methyl or ethyl group andpreferably each R¹ is in the range of Cl₅ to C₁₉;

[0055] 3)

[R_(4−m)−N⁽⁺⁾−R¹ _(m)](X)⁻

[0056] wherein each m is 2 or 3, R¹ and X⁻ have the same meanings asbefore;

[0057] 4)

[0058] wherein each R, R¹, and X⁻ have the definitions given above; eachR² is a C₁₋₆ alkylene group, preferably an ethylene group; and G is anoxygen atom or an —NR— group;

[0059] 5)

[0060] wherein R¹, R² and G are defined as above;

[0061] 6) reaction products of substantially unsaturated and/or branchedchain higher fatty acids with dialkylenetriamines in, e.g., a molecularratio of about 2:1, said reaction products containing compounds of theformula:

R¹—C(O)—NH—R²—NH—R³—NH—C(O)—R¹

[0062] wherein R¹, R² are defined as above, and each R³ is a C₁₋₆alkylene group, preferably an ethylene group;

[0063] 7)

[R¹—C(O)—NR—R²—N(R)₂—R³—NR—C(O)—R¹]⁺X⁻

[0064] wherein R, R¹, R², R³ and X⁻ are defined as above;

[0065] 8) the reaction product of substantially unsaturated and/orbranched chain higher fatty acid with hydroxyalkylalkylenediamines in amolecular ratio of about 2:1, said reaction products containingcompounds of the formula:

R¹—C(O)—NH—R²—N(R³OH)—C(O)—R¹

[0066] wherein R¹, R² and R³ are defined as above;

[0067] 9)

[0068] wherein R, R¹, R², and X⁻ are defined as above;

[0069] 10) acyclic quaternary ammonium salts having the formula:

[R¹—N(R⁵)₂—R⁶]⁺X⁻

[0070] wherein R⁵ and R⁶ are C₁-C₄ alkyl or hydroxyalkyl groups, and R¹and X— are defined as herein above;

[0071] 11) substituted imidazolinium salts having the formula:

[0072] wherein R⁷ is hydrogen or a C₁-C₄ saturated alkyl or hydroxyalkylgroup, and R¹ and X⁻ are defined as hereinabove;

[0073] 12) substituted imidazolinium salts having the formula:

[0074] wherein R⁵ is a C₁-C₄ alkyl or hydroxyalkyl group, and R¹, R²,and X⁻ are as defined above;

[0075] 13) alkylpyridinium salts having the formula:

[0076] wherein R¹ and X⁻ are defined as herein above;

[0077] 14) alkanamide alkylene pyridinium salts having the formula:

[0078] wherein R¹, R² and X⁻ are defined as herein above; and.

[0079] 15) mixtures thereof.

[0080] The above compounds preferably have a phase transitiontemperature of less than about 50° C., more preferably less than about35° C., even more preferably less than about 20° C., and yet even morepreferably less than about 0° C. Fabric softening compounds having suchphase transition temperatures are easier to process, provide fabricshaving improved water absorption properties, and provide superior fabricfeel.

[0081] The present invention also relates to fabric softeningcompositions containing, as an essential component, from about 2% toabout 80%, preferably from about 13% to about 75%, more preferably fromabout 15% to about 70%, and even more preferably from about 19% to about65%, by weight of the composition, of said fabric softener actives, saidfabric softener actives being selected from the compounds identifiedhereinbefore, and mixtures thereof. These fabric softening compositionscontains:

[0082] A) from about 2% to about 80%, preferably from about 13% to about75%, more preferably from about 15% to about 70%, and even morepreferably from about 19% to about 65%, by weight of the composition, ofbiodegradable fabric softener active identified hereinbefore

[0083] B) optionally, but preferably, the compositions can also containan effective amount to improve clarity, less than about 40%, morepreferably from about 10% to about 35%, more preferably from about 12%to about 25%, and even more preferably from about 14% to about 20%, byweight of the composition of principal solvent having a ClogP of fromabout −2.0 to about 2.6, more preferably from about −1.7 to about 1.6,and even more preferably from about −1.0 to about 1.0, as definedhereinafter” said principal solvent preferably selected from the groupconsisting of: 2,2,4-trimethyl-1,3-pentane diol; the ethoxylate,diethoxylate, or triethoxylate derivatives of2,2,4-trimethyl-1,3-pentane diol; 2-ethylhexyl-1,3-diol; the ethoxylate,diethoxylate, or triethoxylate derivatives of 2-ethylhexyl-1,3-diol; 1,2hexanediol; hexylene glycol; and mixtures thereofto provide a clearproduct;

[0084] C) optionally, but preferably, an effective amount, sufficient toimprove clarity, of low molecular weight water soluble solvents likeethanol, isopropanol, propylene glycol, 1,3-propanediol, propylenecarbonate, etc., said water soluble solvents being at a level that willnot form clear compositions by themselves;

[0085] D) optionally, but preferably, an effective amount to improveclarity, of water soluble calcium and/or magnesium salt, preferablychloride; and

[0086] E) the balance being water.

[0087] Preferably, the fabric softening compositions herein are aqueous,translucent or clear, preferably clear, compositions containing fromabout 3% to about 95%, preferably from about 10% to about 80%, morepreferably from about 30% to about 70%, and even more preferably fromabout 40% to about 60%, water and from about 3% to about 40%, preferablyfrom about 10% to about 35%, more preferably from about 12% to about25%, and even more preferably from about 14% to about 20%, of the aboveprincipal alcohol solvent B. These preferred products (fabric softeningcompositions) are not translucent, or clear, without principal solventB. The amount of principal solvent B. required to make the compositionstranslucent, or clear, is preferably more than 50%, more preferably morethan about 60%, and even more preferably more than about 75%, of thetotal organic solvent present.

[0088] The fabric softening compositions can also be prepared asconventional dispersions of the fabric softener active containing fromabout 2% to about 50%, preferably from about 10% to about 40%, morepreferably from about 15% to about 30%, of the fabric softener active.The fabric softening compositions can also be prepared as solids, eithergranular, or attached to substrates, as disclosed hereinafter.

[0089] The pH of the aqueous fabric softening compositions should befrom about 1 to about 7, preferably from about 1.5 to about 5, morepreferably from about 2 to about 3.5.

[0090] All percentages and proportions herein are by weight unlessotherwise indicated. All documents are incorporated, in their relevantpart, by reference.

DETAILED DESCRIPTION OF THE INVENTION

[0091] Highly preferred for the purpose of consumer cleaning productssuch as laundry detergents and personal care compositions of theinvention, are the fatty acids and the salts identified hereinabove. Theesters are not comparable in their utility for such products but may beuseful as intermediates and in fabric conditioners and non-laundryapplications also described herein.

[0092] As used herein the term branched carboxylic acid includes notonly the branched carboxylic acid but also any stereoisomers, loweralkyl esters (preferably C1-C3, more preferably methyl esters) and salts(preferably sodium, potassium, ammonium, substituted ammonium, aluminum,zinc, calcium and magnesium salts). The composition of matter may alsoinclude mixtures, see herein after, for example, mixtures of acid,esters and salts with different or identical carbon chains. Thecomposition of matter herein can be used alone, in mixtures with eachother in any proportion, or in mixtures with any known (conventional)materials such as those disclosed in the background. We distinguishherein between (I) levels of any inventive compound in, on one hand, amixture containing only the composition of matter or its mixtures withother conventional fatty acids or their derivatives and (II) levels ofany composition of matter, or mixture containing same, in afully-formulated consumer product. In terms of (I), levels suitableherein are typically about 1% or higher, preferably 5% or higher, morepreferably 10% or higher, and commonly up to about 51% to 99.9%.

[0093] The invention also encompasses mixtures of the composition ofmatter(s) with known materials, i.e., levels are of the type (II). Suchcompositions include a composition comprising (new material) (i) fromabout 5% to about 99.9% of compounds according to any one or more of theten aspects defined above; said composition further comprising(conventional materiel) (ii) from about 5% to about 95% of conventionalcompounds selected from linear fatty acid compounds or the C1-C3 alkylesters (preferably methyl esters) or salts (preferably sodium,potassium, ammonium, substituted ammonium, aluminum, zinc, calcium andmagnesium salts) of any of said (conventional) compounds. Alternatively,the conventional linear materials can be replaced by, or mixed with toprovide comparable proportions, conventional alkyl-substituted fattyacid compounds or the stereoisomers, C1-C3 alkyl esters (preferablymethyl esters) and salts (preferably sodium, potassium, ammonium,substituted ammonium, aluminum, zinc, calcium and magnesium salts) ofany of said (conventional alkyl-substituted) compounds; and mixturesthereof.

[0094] To further illustrate, conventional alkyl-substituted fatty acidcompounds (see background) permit the present invention to include amixture of composition of the matter and further comprising from about0.1% to about 95% of said conventional compounds, (ii), selected fromthe group consisting of: 2-methyl, 3-methyl, 4-methyl, 5-methyl,6-methyl, 7-methyl, 8-methyl and 9-methyldecanoic acid; 2-methyl,3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl, 9-methyl and10-methylundecanoic acid; 2-methyl, 3-methyl, 4-methyl, 5-methyl,6-methyl, 7-methyl, 8-methyl, 9-methyl, 10-methyl and11-methyldodecanoic acid; 2-methyl, 3-methyl, 4-methyl, 5-methyl,8-methyl, 9-methyl, 11-methyl and 12-methyltridecanoic acid; 2-methyl,3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl, 9-methyl,10-methyl, 11-methyl, 12-methyl and 13-methyltetradecanoic acid;2-methyl, 3-methyl, 4-methyl, 6-methyl, 7-methyl, 10-methyl, 11-methyl,12-methyl, 13-methyl and 14-methylpentadecanoic acid; 2-methyl,3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl, 9-methyl,10-methyl, 11-methyl, 12-methyl, 13-methyl, 14-methyl and15-methylhexadecanoic acid; 2-methyl, 3-methyl, 4-methyl, 5-methyl,6-methyl, 7-methyl, 8-methyl, 9-methyl, 10-methyl, 11-methyl, 12-methyl,13-methyl, 14-methyl, 15-methyl and 16-methylheptadecanoic acid;2-methyl, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl,9-methyl, 10-methyl, 11-methyl, 12-methyl, 13-methyl, 14-methyl,15-methyl, 16-methyl and 17-methyloctadecanoic acid; 2-methyl, 3-methyl,4-methyl, 10-methyl, 17-methyl and 18-methylnonadecanoic acid; and thestereoisomers, C1-C3 alkyl esters (preferably methyl esters) and salts(preferably sodium, potassium, ammonium, substituted ammonium, aluminum,zinc, calcium and magnesium salts) of any of these compounds.

[0095] Certain very valuable mixtures of the invention are furtherillustrated by: a composition wherein the composition of matterincludes:

[0096] one or more branched carboxylic acid of (b) and one or morebranched carboxylic acid of (c) and one or more branched carboxylic acidof (i), optionally complemented by one or more branched carboxylic acidof (a);

[0097] one or more compounds branched carboxylic acid of (b), (d), (g)and (h) aspects optionally complemented by one or more branchedcarboxylic acid of (a);

[0098] one or more branched carboxylic acid of (b), (c), (d), (g) and(h) aspects optionally complemented by one or more branched carboxylicacid of (a); and

[0099] one or more branched carboxylic acid of (b), (c), (d), (g), (h)and (i) aspects optionally complemented by one or more branchedcarboxylic acid of (a)

[0100] Other mixture-type compositions can include only differentcompounds of a single group of branched carboxylic acids, such as amixture of branched carboxylic acids of (j); or any mixture in anyproportions of any branched carboxylic acid of any of the branchedcarboxylic acids of (a)-(k) with any known branched fatty acids, whethersaturated or unsaturated, including isostearic acid, isopalmitic acid ortheir unsaturated analogs.

[0101] Also encompassed by way of mixtures is a composition comprising(i) at least about 1% of the composition of matter of any one or more ofthe branched carboxylic acids (a)-(k) in said salt form; and (iii) atleast about 1% of conventional fatty acids in salt form.

[0102] In terms of preferred composition of matter, there are alsoincluded herein any of the composition of matter being substantiallyfree (the term generally meaning about 0.2% or less, or onlyadventitious amounts) of quaternary-carbon containing fatty acids ortheir salts or derivatives. Such materials reduce biodegradability ofthe compositions.

[0103] Another preferred composition comprises a mixture of thecomposition of matter of any one or more of the branched carboxylicacids (a)-(k) in which there are present at least some of the branchedcarboxylic acids which have an odd total number of carbon atoms, and atleast some of the branched carboxylic acids having an even total numberof carbon atoms.

[0104] In terms of the range in total carbon atoms in the composition ofmatter, the invention preferably encompasses a composition a mixture ofthe branched carboxylic acids (a)-(k), each of the branched carboxylicacids having a total of from 12 carbon atoms to 20 carbon atoms, morepreferably from 14 carbon atoms to 19 carbon atoms, even more preferablyfrom 15 carbon atoms to 18 carbon atoms.

[0105] Another preferred composition of the invention is based on any ofthe branched carboxylic acids (a)-(k), alone or in mixtures withconventional fatty acid derivatives and comprising a mixture of thecompounds, the mixture containing not more than about 0.1% by weight ofcompounds having 12 or fewer, preferably not more than about 14 orfewer, carbon atoms.

[0106] Yet another preferred composition is a mixture of the compositionof matter(or mixtures thereof with conventional fatty acids orderivatives) wherein any alkyl substituent in any of said compounds ismethyl.

[0107] Another preferred composition of the invention is based on any ofthe branched carboxylic acids (a)-(k), in combination with conventionaladditives to form cleaning compositions, skin care compositions andpersonal cleansing compositions. The cleaning composition wouldcomprise:

[0108] (i) from about 0.05% to about 99.9%, preferably 0.5% to about95%, more preferably 1% to about 90%, even more preferably 5% to about75% by weight of a composition of mater, namely any of the branchedcarboxylic acids (a)-(k), alone or in mixtures; and

[0109] (ii) from about 0.0001 to about 99.99%, preferably 0.5% to about95%, more preferably 1% to about 90%, even more preferably 5% to about80% by weight of conventional cleaning additive. The skin carecomposition would comprise:

[0110] (i) from about 0.05% to about 99.9%, preferably 0.5% to about95%, more preferably 1% to about 90%, even more preferably 5% to about75% by weight of a composition of mater namely any of the branchedcarboxylic acids (a)-(k), alone or in mixtures; and

[0111] (ii) from about 0.0001 to about 99.99%, preferably 0.5% to about95%, more preferably 1% to about 90%, even more preferably 5% to about75% by weight of a conventional skin care additive.

[0112] The personal cleansing composition would comprise:

[0113] (i) from about 0.05% to about 99.9%, preferably 0.5% to about95%, more preferably 1% to about 90%, even more preferably 5% to about75% by weight of a composition of mater namely any of the branchedcarboxylic acids (a)-(k), alone or in mixtures; and

[0114] (ii) from about 0.0001 to about 99.99%, preferably 0.5% to about95%, more preferably 1% to about 90%, even more preferably 5% to about75% by weight of a conventional personal cleansing additive.

[0115] Another preferred composition of the invention is paper articlecomprising at least about 0.0001% by weight of said composition ofmatter namely any of the branched carboxylic acids (a)-(k), alone or inmixtures. The paper article can be any conventional paper article wellknown in the art. This paper article can be in the form of a toilettissue, a disposable tissue or disposable wipe.

[0116] It is also preferred that the composition of mater namely any ofthe branched carboxylic acids (a)-(k), alone or in mixtures comprise nomore than about 0.1% aldehyde impurity. Furthermore, it is preferredthat the composition of mater namely any of the branched carboxylicacids (a)-(k), alone or in mixtures comprise no more than about 0.1%unsaturated impurity.

[0117] It is also preferred that composition of mater namely any of thebranched carboxylic acids (a)-(k), alone or in mixtures has at least10%, more preferably of the branched carboxylic acid has from 16 to 17carbon atoms in total. It is also preferred that the composition ofmater namely any of the branched carboxylic acids (a)-(k), alone or inmixtures comprises a mixture of at least six, more preferably 20, evenmore preferably 40, of the branched carboxylic acid.

[0118] The fabric softening compositions described hereinbefore canoptionally, but preferably comprise less than about 40%, preferably fromabout 10% to about 35%, more preferably from about 12% to about 25%, andeven more preferably from about 14% to about 20%, of the principalsolvent, by weight of the composition. Said principal solvent isselected to minimize solvent odor impact in the composition and toprovide a low viscosity to the final composition.

[0119] The suitability of any principal solvent for the formulation ofthe liquid, concentrated, preferably clear, fabric softener compositionsherein with the requisite stability is surprisingly selective. Suitablesolvents can be selected based upon their octanol/water partitioncoefficient (P). Octanol/water partition coefficient of a principalsolvent is the ratio between its equilibrium concentration in octanoland in water. The partition coefficients of the principal solventingredients of this invention are conveniently given in the form oftheir logarithm to the base 10, logP.

[0120] The logP of many ingredients has been reported; for example, thePomona92 database, available from Daylight Chemical Information Systems,Inc. (Daylight CIS), Irvine, Calif., contains many, along with citationsto the original literature. However, the logP values are mostconveniently calculated by the “CLOGP” program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona92 database. The “calculated logP” (ClogP) isdetermined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J.B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each ingredient, and takes into account thenumbers and types of atoms, the atom connectivity, and chemical bonding.These ClogP values, which are the most reliable and widely usedestimates for this physicochemical property, are preferably used insteadof the experimental logP values in the selection of the principalsolvent ingredients which are useful in the present invention. Othermethods that can be used to compute ClogP include, e.g., Crippen'sfragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21(1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf.Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J.Med. Chem.—Chim. Theor., 19, 71 (1984).The principal solvents herein areselected from those having a ClogP of from about 0.15 to about 0.64,preferably from about 0.25 to about 0.62, and more preferably from about0.40 to about 0.60, said principal solvent preferably being at leastsomewhat asymmetric, and preferably having a melting, or solidification,point that allows it to be liquid at, or near room temperature. Solventsthat have a low molecular weight and are biodegradable are alsodesirable for some purposes. The more asymmetric solvents appear to bevery desirable, whereas the highly symmetrical solvents such as1,7-heptanediol, or 1,4-bis(hydroxymethyl) cyclohexane, which have acenter of symmetry, appear to be unable to provide the essential clearcompositions when used alone, even though their ClogP values fall in thepreferred range.

[0121] The most preferred principal solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active. The compositions also inherentlyprovide improved perfume deposition as compared to conventional fabricsoftening compositions, especially when the perfume is added to thecompositions at, or near, room temperature.

[0122] A comprehensive list of possible principal solvents can be foundin U.S. Pat. No. 5,747,443, which is incorporated herein by reference.

[0123] The above fabric softeners can also be combined with other fabricsofteners, such as, those in U.S. Pat. No. 3,861,870, Edwards and Diehl;U.S. Pat. No. 4,308,151, Cambre; U.S. Pat. No. 3,886,075, Bernardino;U.S. Pat. No. 4,233,164, Davis; U.S. Pat. No. 4,401,578, Verbruggen;U.S. Pat. No. 3,974,076, Wiersema and Rieke; and U.S. Pat. No.4,237,016, Rudkin, Clint, and Young, all of said patents beingincorporated herein by reference. The additional softener actives hereinare preferably those that are highly branched and/or unsaturatedversions of the traditional softener actives, i.e., di-long chain alkylnitrogen derivatives, normally cationic materials, such asdioleyldimethylammonium chloride and imidazolinium compounds asdescribed hereinafter. Examples of more biodegradable fabric softenerscan be found in U.S. Pat. No. 3,408,361, Mannheimer, issued Oct. 29,1968; U.S. Pat. No. 4,709,045, Kubo et al., issued Nov. 24, 1987; U.S.Pat. No. 4,233,451, Pracht et al., issued Nov. 11, 1980; U.S. Pat. No.4,127,489, Pracht et al., issued Nov. 28, 1979; U.S. Pat. No. 3,689,424,Berg et al., issued Sep. 5, 1972; U.S. Pat. No. 4,128,485, Baumann etal., issued Dec. 5, 1978; U.S. Pat. No. 4,161,604, Elster et al., issuedJul. 17, 1979; U.S. Pat. No. 4,189,593, Wechsler et al., issued Feb. 19,1980; and U.S. Pat. No. 4,339,391, Hoffman et al., issued Jul. 13, 1982,said patents being incorporated herein by reference.

[0124] An example of Compound 4. is1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methylsulfate wherein R¹is as defined above, R² is an ethylene group, G is a NH group, R⁵ is amethyl group and X⁻ is a methyl sulfate anion.

[0125] An example of Compound 5. is 1-oleylamidoethyl-2-oleylimidazolinewherein R¹ is as defined above, R² is an ethylene group, and G is a NHgroup.

[0126] An example of Compound 6. is reaction products of oleic acidswith diethylenetriamine in a molecular ratio of about 2:1, said reactionproduct mixture containing N,N″-dioleoyldiethylenetriamine with theformula:

R¹—C(O)—NH—CH₂CH₂—NH—CH₂CH₂—NH—C(O)—R¹

[0127] wherein R¹—C(O) is oleoyl group of any of the novel branchedacids described herein or any commercially available oleic acid derivedfrom a vegetable or animal source, such as Emersol® 223LL or Emersol®7021, available from Henkel Corporation, and R² and R³ are divalentethylene groups.

[0128] An example of Compound 7. is a difatty amidoamine based softenerhaving the formula:

[R¹—C(O)—NH—CH₂CH₂—N(CH₃)(CH₂CH₂OH)—CH₂CH₂—NH—C(O)—R¹]+CH₃SO₄ ⁻

[0129] wherein R¹—C(O) is oleoyl group of any of the novel branchedacids described herein or any commercially available oleic acid derivedfrom a vegetable or animal source.

[0130] An example of Compound 8. is reaction products of oleic acidswith N-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1,said reaction product mixture containing a compound of the formula:

R¹—C(O)—NH—CH₂CH₂—N(CH₂CH₂OH)—C(O)—R¹

[0131] wherein R¹—C(O) is oleoyl group of any of the novel branchedacids described herein or any commercially available oleic acid derivedfrom a vegetable or animal source such as Emersol® 223LL or Emersol®7021, available from Henkel Corporation.

[0132] An example of Compound 9. is the diquaternary compound having theformula:

[0133] wherein R¹ is oleoyl group of any of the novel branched acidsdescribed herein.

[0134] An example of Compound 13. is1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfatewherein R¹ is as defined above, R² is an ethylene group, R⁵ is an ethylgroup, and X⁻ is an ethylsulfate anion.

[0135] The invention has numerous additional useful embodiments asdescribed and illustrated in the examples, detergent examples and claimshereinafter.

General Procedure I

[0136]

General Procedure II

[0137]

General Procedure III

[0138]

General Procedure IV

[0139]

General Procedure V

[0140]

General Procedure VI

[0141]

General Procedure VII

[0142]

General Procedure VIII

[0143]

EXAMPLE 1 5-methylpentadecanoic Acid

[0144] See GENERAL PROCEDURE I. Decyl bromide (compound (1),R═CH₃(CH₂)₉₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with carbon dioxide and aqueousacidic workup (I, Step (f)) followed by catalytic hydrogenation (Pdcatalyst) to form 5-methylpentadecanoic acid, (5).

EXAMPLE 2 7-methyltridecanoic Acid

[0145] See GENERAL PROCEDURE I. Hexyl bromide (compound (1),R═CH₃(CH₂)₅₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₅₋). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)),hydrogenation (I, Step (i)), Pd catalyst, and hydrobromination (I, Step(j)). The alkyl bromide (6) (R═CH₃(CH₂)₅₋, y=5) is converted to theGrignard reagent with magnesium (I, Step (k)), which is treated withcarbon dioxide and aqueous acidic workup (I, Step (1)) to give theproduct, 7-methyltridecanoic acid, (7).

EXAMPLE 3 8-methylpentadecanoic Acid

[0146] See GENERAL PROCEDURE I. Heptyl bromide (compound (1),R═CH₃(CH₂)₆₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₆₋). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)),hydrogenation (I, Step (i)), Pd catalyst, and hydrobromination (I, Step(j)). The alkyl bromide (6) (R═CH₃(CH₂)₆₋, y=5) is converted to theGrignard reagent with magnesium (I, Step (k)), which is treated withformaldehyde, and aqueous workup (I, Step (m). Alkyl halide (8)(R═CH₃(CH₂)₆₋, x=6) is formed by hydrobromination (I, Step (O)). This isconverted to its Grignard reagent with magnesium in dry ether (I, Step(p)) followed by treatment with carbon dioxide and aqueous acidic workup(I, Step (q)) to give the product, 8-methylpentadecanoic acid, (9).

EXAMPLE 4 9-methylpentadecanoic Acid

[0147] See GENERAL PROCEDURE I. Hexyl bromide (compound (1),R═CH₃(CH₂)₅₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₅₋). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)),hydrogenation (I, Step (i)), Pd catalyst, and hydrobromination (I, Step(O)). The alkyl bromide (6) (R═CH₃(CH₂)₅₋, y=5) is converted to theGrignard reagent with magnesium (I, Step (k)) which is treated withethylene oxide and aqueous acidic workup (I, Step (h)) andhydrobromination (I, Step (j)). The alkyl bromide (6) (R═CH₃(CH₂)₅₋,y=7) is converted to the Grignard reagent with magnesium (I, Step (k))which is treated with carbon dioxide and aqueous acidic workup (I, Step(l)) to give the product, 9-methylpentadecanoic acid, (7).

EXAMPLE 5 10-methyltridecanoic Acid

[0148] See GENERAL PROCEDURE I. 1-propyl bromide (compound (1),R═CH₃(CH₂)₂₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₂₋). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)),hydrogenation (I, Step (i)), Pd catalyst, and hydrobromination (I, Step(j)). The alkyl bromide (6) (R═CH₃(CH₂)₂₋, y=5) is converted to theGrignard reagent with magnesium (I, Step (k)). Departing from GeneralProcedure I, this Grignard reagent is again treated with ethylene oxidefollowed by aqueous acidic workup and hydrobromination. The intermediatealkyl bromide, CH₃(CH₂)₂CH(Me)(CH₂)₇Br, is converted to the Grignardreagent with magnesium, which, returning to the general procedure I atstep (I m), is treated with formaldehyde, and aqueous workup (I, Step(m). Alkyl halide (8) (R═CH₃(CH₂)₂₋, x=8) is formed by hydrobromination(I, Step (O)). This is converted to its Grignard reagent with magnesiumin dry ether (I, Step (p)) followed by treatment with carbon dioxide andaqueous acidic workup (I, Step (q)) to give the product,10-methyltridecanoic acid, (9).

EXAMPLE 6 6-propyltetradecanoic Acid

[0149] Following General Procedure VIII use 1-bromopropane in step (c)(Z=CH₃(CH₂)₂₋) and use 1-bromohexane in step (f) (R═CH₃(CH₂)₅₋) toeventually obtain 2-propyl-1-decanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n−1), (O), (p), (n−2), (O), (p) (that is, oneethylene oxide iteration and one formaldehyde iteration) gives finalGrignard reagent (12), x=4, R=n-hexyl, Z=n-Pr which with CO₂ treatmentgives 6-propyltetradecanoic acid (13) (x=4, R=n-hexyl, Z=n-Pr).

EXAMPLE 7 8-ethylpentadecanoic Acid

[0150] Following General Procedure VIII use ethyl bromide in step (c)(Z=CH₃CH₂₋) and use I-bromopentane in step (f) (R═CH₃(CH₂)₄₋) toeventually obtain 2-ethyl-1-nonanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n−1), (O), (p), (n−1), (O), (p), (n−2), (O), (p)(that is, two ethylene oxide iterations and one formaldehyde iteration)gives final Grignard reagent (12), x=6, R=n-pentyl, Z=Et which with CO₂treatment gives 8-ethylpentadecanoic acid (13) (x=6, R=n-pentyl, Z=Et).

EXAMPLE 8 6-methyltridecanoic Acid

[0151] See GENERAL PROCEDURE I. Heptyl bromide (compound (1),R═CH₃(CH₂)₆₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₆₋). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). This is treated with formaldehyde stepand aqueous workup (I m), hydrogenation (I n). Alkyl halide (8)(R═CH₃(CH₂)₆₋, x=4) is formed by hydrobromination (I, Step (O)). This isconverted to its Grignard reagent with magnesium in dry ether (I, Step(p)) followed by treatment with carbon dioxide and aqueous acidic workup(I, Step (q)) to give the product, 6-methyltridecanoic acid, (9).

EXAMPLE 9 2,5-dimethyltetradecanoic Acid

[0152] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+ equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

[0153] A Grignard reagent is made from 2-bromoundecane and magnesium(II, step (f)) which is treated (II, step (g)) with cadmium chloride toform the corresponding dialkylcadmium, di(2-undecyl)cadmium, (5).

[0154] The dialkylcadmium reagent (5) is allowed to react with the acidchloride compound (4) (II, step (h)) to form (6) (R=2-undecyl). This ishydrolyzed to the corresponding keto-acid (7) which is reduced eitherwith the Wolff-Kishner or, Clemmensen reductions II, step (1)) to give2,5-dimethyltetradecanoic acid.

EXAMPLE 10 2,7-dimethyltetradecanoic Acid

[0155] The compound is prepared from 2-nonyl bromide (1) and succinicanhydride using Procedure III. y=2.

EXAMPLE 11 2,9-dimethyltetradecanoic Acid

[0156] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

[0157] Now see GENERAL PROCEDURE I. 1-pentyl bromide (compound (1),R═CH₃(CH₂)₄₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₄₋). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withformaldehyde and aqueous workup (I, Step (m)) and hydrogenated (I, Step(n)), Pd catalyst, and hydrobrominated (I, Step (O)) to give the alkylbromide (8) (R═CH₃(CH₂)₄₋, x=4). Now this compound (8) of Procedure I iscarried over and used following part of the procedure shown in GENERALPROCEDURE II, as an alkyl halide and is converted to the Grignardreagent with magnesium (II, Step (f)). The Grignard reagent is convertedto a dialkylcadmium (5), di(5-methyl-1-decyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-decyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step 0)) to give2,9-dimethyltetradecanoic acid.

EXAMPLE 12 2,11-dimethyltetradecanoic Acid

[0158] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+ equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

[0159] Now see GENERAL PROCEDURE I. 1-propyl bromide (compound (1),R═CH₃(CH₂)₂₋) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₂₋). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withformaldehyde and aqueous workup (I, Step (m)) and hydrogenated (I, Step(n)), Pd catalyst, and hydrobrominated (I, Step (O)) to give the alkylbromide (8) (R═CH₃(CH₂)₂₋, x=4). Now following another part of theprocedure shown in GENERAL PROCEDURE I, compound (8) is used instead ofcompound (4) of Procedure I as an alkyl halide and is converted to aGrignard reagent with magnesium (I, Step (e)). The Grignard reagent istreated with ethylene oxide followed by aqueous acidic workup (I, Step(h)), and hydrobromination (I, Step 0)), to give compound (6)(R=7-methyl-1-decyl, y=6). Now this compound (6) is used in another partof the procedure shown in GENERAL PROCEDURE II, namely, step (II, (f))where it is converted to a Grignard reagent. The Grignard reagent isconverted to a dialkylcadmium (5), di(7-methyl-1-decyl)cadmium (II,(g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-decyl-. This is hydrolyzed tothe corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,11-dimethyltetradecanoic acid.

EXAMPLE 13 2,13-dimethyltetradecanoic Acid

[0160] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

[0161] Now see GENERAL PROCEDURE I. Methyl iodide (compound (1)) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃₋). (4) is converted to itsGrignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8) (R═CH₃₋,x=4). Now following another part of the procedure shown in GENERALPROCEDURE I, compound (8) is used instead of compound (4) of Procedure Ias an alkyl halide and is converted to a Grignard reagent with magnesium(I, Step (e)). The Grignard reagent is treated with ethylene oxidefollowed by aqueous acidic workup (I, Step (h)), and hydrobromination(I, Step (j)), to give compound (6) (R=Methyl, y=6). In a secondGrignard/ethylene oxide loop, compound (6) is converted to its Grignardreagent, treated with ethylene oxide followed by aqueous acidic workup(I, Step (h)), and hydrobromination (I, Step (j)), to give a newcompound (6) (R=Methyl, y=8).

[0162] Now this compound (6) is used in another part of the procedureshown in GENERAL PROCEDURE II, namely, step (II, (f)) where it isconverted to a Grignard reagent. The Grignard reagent is converted to adialkylcadmium (5), di(9-methyl-1-decyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=9-methyl-1-decyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,13-dimethyltetradecanoic acid.

EXAMPLE 14 2,15-dimethylhexadecanoic Acid

[0163] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

[0164] Now see GENERAL PROCEDURE I. Methyl iodide (compound (1)) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃₋). (4) is converted to itsGrignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8) (R═CH₃₋,x=4). Now following another part of the procedure shown in GENERALPROCEDURE I, compound (8) is used instead of compound (4) of Procedure Ias an alkyl halide and is converted to a Grignard reagent with magnesium(I, Step (e)). The Grignard reagent is treated with ethylene oxidefollowed by aqueous acidic workup (I, Step (h)), and hydrobromination(I, Step (j)), to give compound (6) (R=Methyl, y=6). In two additionalGrignardlethylene oxide loops, compound (6) is converted to Grignardreagent, treated with ethylene oxide followed by aqueous acidic workup(I, Step (h)), and hydrobromination (I, Step (j)), ultimately givingcompound (6) (R=Methyl, y=10). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(1′-methyl-1-dodecyl)cadmium(II, (g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=11-methyl-1-dodecyl-. This is hydrolyzedto the corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,15-dimethylhexadecanoic acid.

EXAMPLE 15 2,17-dimethyloctadecanoic Acid

[0165] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+ equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

[0166] Now see GENERAL PROCEDURE I. Methyl bromide (compound (1)) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃₋). (4) is converted to itsGrignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8) (R═CH₃₋,x=4). Now following another part of the procedure shown in GENERALPROCEDURE I, compound (8) is used instead of compound (4) of Procedure Ias an alkyl halide and is converted to a Grignard reagent with magnesium(I, Step (e)). The Grignard reagent is treated with ethylene oxidefollowed by aqueous acidic workup (I, Step (h)), and hydrobromination(I, Step (j)), to give compound (6) (R=Methyl, y=6). In threeGrignard/ethylene oxide loops, compound (6) is converted to Grignardreagent, treated with ethylene oxide followed by aqueous acidic workup(I, Step (h)), and hydrobromination (I, Step (j)), ultimately givingcompound (6) (R=Methyl, y=12). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5),R=di(13-methyl-1-tetradecyl)cadmium (II, (g)). The dialkylcadmium isreacted (II, step (h)) with the acid chloride of 2-methylsuccinic acid1-methyl ester (compound (4) prepared supra) yielding compound (6),R=13-methyl-1-tetradecyl-. This is hydrolyzed to the correspondingketo-acid (7) which is reduced either with the Wolff-Kishner orClemmensen reductions (II, step (j)) to give 2,17-dimethyloctadecanoicacid.

EXAMPLE 16 2,5-Dimethylpentadecanoic Acid

[0167] The compound is made using the following variations with respectto Example 9: The alkyl halide is 2-bromododecane in replacement for2-bromoundecane in Example 9. The Cd intermediate isdi(2-dodecyl)cadmium. The product is 2,5-dimethylpentadecanoic acid.

EXAMPLE 17 2,5-Dimethylhexadecanoic Acid

[0168] The compound is made using the following variations with respectto Example 9: The alkyl halide is 2-bromotridecane in replacement for2-bromoundecane in Example 9. The Cd intermediate isdi(2-tridecyl)cadmium. The product is 2,5-dimethylhexadecanoic acid.

EXAMPLE 18 2,5-Dimethyloctadecanoic Acid

[0169] The compound is made using the following variations with respectto Example 9: The alkyl halide is 2-bromopentadecane in replacement for2-bromoundecane in Example 9. The Cd intermediate isdi(2-pentadecyl)cadmium. The product is 2,5-dimethyloctadecanoic acid.

EXAMPLE 19 2,7-Dimethylpentadecanoic Acid

[0170] The compound is made using the following variations with respectto Example 10: The alkyl halide is 2-bromodecane. y=2.

EXAMPLE 20 2,7-Dimethylhexadecanoic Acid

[0171] The compound is made using the following variations with respectto Example 10: The alkyl halide is 2-bromoundecane. y=2.

EXAMPLE 21 2,7-Dimethylheptadecanoic Acid

[0172] The compound is made using the following variations with respectto Example 10: The alkyl halide is 2-bromododecane. y=2.

EXAMPLE 22 2,7-Dimethyloctadecanoic Acid

[0173] The compound is made using the following variations with respectto Example 10: The alkyl halide is 2-bromotridecane. y=2.

EXAMPLE 23 2,9-Dimethylpentadecanoic Acid

[0174] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-hexyl bromide (compound (1), R═CH₃(CH₂)₅₋) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₅₋). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₅₋, x=4). Now this compound (8) of Procedure I is carriedover and used following part of the procedure shown in GENERAL PROCEDUREII, as an alkyl halide and is converted to the Grignard reagent withmagnesium (II, Step (f)). The Grignard reagent is converted to adialkylcadmium (5), di(5-methyl-1-undecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-undecyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step 0)) to give2,9-Dimethylpentadecanoic acid.

EXAMPLE 24 2,9-Dimethylhexadecanoic Acid

[0175] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+ equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-heptyl bromide (compound (1), R═CH₃(CH₂)₆₋)is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (I,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₆₋). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with formaldehyde and aqueousworkup (I, Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8)(R═CH₃(CH₂)₆₋, x=4). Now this compound (8) of Procedure I is carriedover and used following part of the procedure shown in GENERAL PROCEDUREII, as an alkyl halide and is converted to the Grignard reagent withmagnesium (II, Step (f)). The Grignard reagent is converted to adialkylcadmium (5), di(5-methyl-1-dodecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-dodecyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step 0)) to give2,9-Dimethylhexadecanoic acid.

EXAMPLE 25 2,9-Dimethylheptadecanoic Acid

[0176] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+ equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-octyl bromide (compound (1), R═CH₃(CH₂)₇₋) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₇₋). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8)(R═CH₃(CH₂)₇₋, x=4). Now this compound (8) of Procedure I is carriedover and used following part of the procedure shown in GENERAL PROCEDUREII, as an alkyl halide and is converted to the Grignard reagent withmagnesium (II, Step (f)). The Grignard reagent is converted to adialkylcadmium (5), di(5-methyl-1-tridecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-tridecyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,9-dimethyltetradecanoic acid.

EXAMPLE 26 2,11-Dimethylpentadecanoic Acid

[0177] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+ equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-butyl bromide (compound (1), R═CH₃(CH₂)₃₋) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₃₋). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8)(R═CH₃(CH₂)₃₋, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-undecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-undecyl)cadmium (II,(g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-undecyl-. This is hydrolyzedto the corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,11-dimethylpentadecanoic acid.

EXAMPLE 27 2,11-Dimethylhexadecanoic Acid

[0178] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-pentyl bromide (compound (1), R═CH₃(CH₂)₄₋)is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (I,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₄₋). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with formaldehyde and aqueousworkup (I, Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8)(R═CH₃(CH₂)₄₋, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-dodecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-dodecyl)cadmium (II,(g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-dodecyl-. This is hydrolyzedto the corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,11-dimethylhexadecanoic acid.

EXAMPLE 28 2,11-Dimethylheptadecanoic Acid

[0179] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-hexyl bromide (compound (1), R═CH₃(CH₂)₅₋) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₅₋). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₅₋, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-tridecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-tridecyl)cadmium(II, (g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-tridecyl-. This is hydrolyzedto the corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,11-dimethylheptadecanoic acid.

EXAMPLE 29 2,11-Dimethyloctadecanoic Acid

[0180] Succinic anhydride is opened using methanol (II, step (a)) togive monomethyl succinate (2). This is treated with 2+ equivalents oflithium amide in liquid ammonia (II, step (b)) to form its dianion whichis alkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-heptyl bromide (compound (1), R═CH₃(CH₂)₆₋)is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (I,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₆₋). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with formaldehyde and aqueousworkup (I, Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (O)) to give the alkyl bromide (8)(R═CH₃(CH₂)₆₋, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-tetradecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-tetradecyl)cadmium(II, (g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-tetradecyl-. This ishydrolyzed to the corresponding keto-acid (7) which is reduced eitherwith the Wolff-Kishner or Clemmensen reductions (II, step (j)) to give2,11-dimethyloctadecanoic acid.

EXAMPLE 30 2,13-Dimethylpentadecanoic Acid

[0181] The procedure is as described in Example 13 except that EthylBromide replaces Methyl iodide in Step 1a.

EXAMPLE 31 2,13-Dimethylhexadecanoic Acid

[0182] The procedure is as described in Example 13 except that 1-propylBromide replaces Methyl iodide in Step 1a.

EXAMPLE 32 2,13-Dimethylheptadecanoic Acid

[0183] The procedure is as described in Example 13 except that 1-butylBromide replaces Methyl iodide in Step 1a.

EXAMPLE 33 2,13-Dimethyloctadecanoic Acid

[0184] The procedure is as described in Example 13 except that 1-pentylBromide replaces Methyl iodide in Step 1a.

EXAMPLE 34 2,15-Dimethylheptadecanoic Acid

[0185] The procedure is as described in Example 14 except that EthylBromide replaces Methyl iodide in Step 1a.

EXAMPLE 35 2,15-Dimethyloctadecanoic Acid

[0186] The procedure is as described in Example 14 except that 1-propylBromide replaces Methyl iodide in Step 1a.

EXAMPLE 36 2-ethyl-5-methyltetradecanoic Acid

[0187] The procedure is as described in Example 9 except that EthylBromide replaces Methyl Iodide.

EXAMPLE 37 2-ethyl-7-methyltetradecanoic Acid

[0188] The procedure is as described in Example 10 except that EthylBromide replaces Methyl Iodide in step (h).

EXAMPLE 38 2-ethyl-9-methyltetradecanoic Acid

[0189] The procedure is as described in Example 11 except that EthylBromide replaces Methyl Iodide.

EXAMPLE 39 2-ethyl-1-methyltetradecanoic Acid

[0190] The procedure is as described in Example 12 except that EthylBromide replaces Methyl Iodide.

EXAMPLE 40 2-ethyl-13-methyltetradecanoic Acid

[0191] The procedure is as described in Example 13 except that EthylBromide replaces Methyl Iodide.

EXAMPLE 41 2-ethyl-5-methyltridecanoic Acid

[0192] The procedure is as described in Example 9 except that EthylBromide replaces Methyl Iodide and 2-bromodecane replaces2-bromoundecane.

EXAMPLE 42 2-ethyl-7-methyltridecanoic Acid

[0193] The procedure is as described in Example 10 except that EthylBromide replaces Methyl Iodide in step (h) and 2-octyl bromide replaces2-nonyl bromide.

EXAMPLE 43 2-ethyl-9-methyltridecanoic Acid

[0194] The procedure is as described in Example 11 except that EthylBromide replaces Methyl Iodide and 1-bromobutane replaces 1-pentylbromide.

EXAMPLE 44 2-ethyl-11-methyltridecanoic Acid

[0195] The procedure is as described in Example 12 except that EthylBromide replaces Methyl Iodide in procedure II step (c) and ethylbromide also replaces 1-propyl bromide in procedure I step (a).

EXAMPLE 45 2-ethyl-6-methyltetradecanoic Acid

[0196] The procedure used is that of GENERAL PROCEDURE III except that2-bromodecane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and ethyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 46 2-ethyl-6-methyltridecanoic Acid

[0197] The procedure used is that of GENERAL PROCEDURE III except that2-bromononane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and ethyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 47 2-ethyl-8-methyltetradecanoic Acid

[0198] The procedure used is that of GENERAL PROCEDURE IV. j=5, k=1.

EXAMPLE 48 2-ethyl-8-methyltridecanoic Acid

[0199] The procedure used is that of GENERAL PROCEDURE IV. j=4, k=1.

EXAMPLE 49 2-ethyl-10-methyltetradecanoic Acid

[0200] The procedure used is that of GENERAL PROCEDURE IV. j=3, k=2.

EXAMPLE 50 7,8-dimethyltridecanoic Acid

[0201] The procedure used is that of GENERAL PROCEDURE V. x=4, y=2.

EXAMPLE 51 7,8-dimethylpentadecanoic Acid

[0202] The procedure used is that of GENERAL PROCEDURE V. x=6, y=2.

EXAMPLE 52 9,10-dimethylpentadecanoic Acid

[0203] The procedure used is that of GENERAL PROCEDURE V. x=4, y=4.

EXAMPLE 53 9,10-dimethylheptadecanoic Acid

[0204] The procedure used is that of GENERAL PROCEDURE V. x=6, y=4.

EXAMPLE 54 8,9-dimethylpentadecanoic Acid

[0205] The procedure used is that of GENERAL PROCEDURE VI. x=5, y=3.

EXAMPLE 55 2-propyl-5-methyltridecanoic Acid

[0206] The procedure is as described in Example 9 except that PropylBromide replaces Methyl Iodide and 2-bromodecane replaces2-bromoundecane.

EXAMPLE 56 2-propyl-7-methyltridecanoic Acid

[0207] The procedure is as described in Example 10 except that PropylBromide replaces Methyl Iodide and 2-Bromooctane replaces 2-bromononane.y=2.

EXAMPLE 57 2-propyl-9-methyltridecanoic Acid

[0208] The procedure is as described in Example 11 except that PropylBromide replaces Methyl Iodide in step (c) of GENERAL PROCEDURE II and1-butyl bromide replaces 1-pentyl bromide in step (a) of GENERALPROCEDURE I.

EXAMPLE 58 2-propyl-11-methyltridecanoic Acid

[0209] The procedure is as described in Example 12 except that PropylBromide replaces Methyl Iodide in Step IIc and ethyl bromide replaces1-propyl bromide in step 1a.

EXAMPLE 59 2-propyl-5-methyldodecanoic Acid

[0210] The procedure is as described in Example 9 except that PropylBromide replaces Methyl Iodide and 2-bromononane replaces2-bromoundecane.

EXAMPLE 60 2-propyl-7-methyldodecanoic Acid

[0211] The procedure is as described in Example 10 except that PropylBromide replaces Methyl Iodide and 2-bromoheptane replaces2-bromononane. y=2.

EXAMPLE 61 2-propyl-9-methyldodecanoic Acid

[0212] The procedure is as described in Example 11 except that PropylBromide replaces Methyl Iodide in step IIc and 1-propyl bromide replaces1-pentyl bromide in step 1a.

EXAMPLE 62 2-propyl-11-methyldodecanoic Acid

[0213] The procedure is as described in Example 12 except that PropylBromide replaces Methyl Iodide in step IIc and methyl iodide replaces1-propyl bromide in step 1a.

EXAMPLE 63 2-propyl-6-methyltridecanoic Acid

[0214] The procedure used is that of GENERAL PROCEDURE III except that2-bromononane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and propyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 64 2-propyl-6-methyldodecanoic Acid

[0215] The procedure used is that of GENERAL PROCEDURE III except that2-bromooctane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and propyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 65 2-propyl-8-methyltridecanoic Acid

[0216] The procedure used is that of GENERAL PROCEDURE IV. j=4, k=I and1-propyl bromide replaces ethyl bromide.

EXAMPLE 66 2-propyl-8-methyldodecanoic Acid

[0217] The procedure used is that of GENERAL PROCEDURE IV. j=3, k=1 and1-propyl bromide replaces ethyl bromide.

EXAMPLE 67 2-propyl-10-methyltridecanoic Acid

[0218] The procedure used is that of GENERAL PROCEDURE IV. j=2, k=2 and1-propyl bromide replaces ethyl bromide.

EXAMPLE 68 2-propyl-10-methyldodecanoic Acid

[0219] The procedure used is that of GENERAL PROCEDURE IV. j=1, k=2 and1-propyl bromide replaces ethyl bromide.

EXAMPLE 69 6,7-dimethylundecanoic Acid

[0220] The procedure used is that of GENERAL PROCEDURE VII starting with2-bromohexane; x=3, y=1.

EXAMPLE 70 9-ethyltridecanoic Acid

[0221] Following General Procedure VIII use ethyl bromide in step (c)(Z=CH₃CH₂₋) and use ethyl bromide in step (f) (R═CH₃CH₂₋) to eventuallyobtain 2-ethyl-1-hexanol as compound (9). This is converted to itsbromide in step (1) and to its Grignard reagent in step (m). Followingthe sequence (n−1), (o), (p), (n−1), (o), (p), (n−1), (o), (p) (that is,three iterations of ethylene oxide) gives final Grignard reagent (12),x=7, R=Et, Z=Et which with CO₂ treatment gives 9-ethyltridecanoic acid(13) (x=7, R=Et, Z=Et).

EXAMPLE 71 9-propyldodecanoic Acid

[0222] Following General Procedure VIII use 1-bromopropane in step (c)(Z=CH₃(CH₂)₂₋) and use methyl bromide in step (f) (R═CH₃₋) to eventuallyobtain 2-propyl-1-pentanol as compound (9). This is converted to itsbromide in step (I) and to its Grignard reagent in step (m). Followingthe sequence (n−1), (o), (p), (n−1), (o), (p), (n−1), (O), (p) (that is,three iterations of ethylene oxide) gives final Grignard reagent (12),x=7, R=Me, Z=n-Pr which with CO₂ treatment gives 9-propyldodecanoic acid(13) (x=7, R=Me, Z=n-Pr).

EXAMPLE 72 9-ethylpentadecanoic Acid

[0223] Following General Procedure VIII use ethyl bromide in step (c)(Z=CH₃CH₂₋) and use I-bromobutane in step (f) (R═CH₃(CH₂)₃₋) toeventually obtain 2-ethyl-1-octanol as compound (9). This is convertedto its bromide in step (l) and to its Grignard reagent in step (m).Following the sequence (n−1), (o), (p), (n−1), (O), (p), (n−1), (o), (p)(that is, three iterations of ethylene oxide) gives final Grignardreagent (12), x=7, R=n-Bu, Z=Et which with CO₂ treatment gives9-ethylpentadecanoic acid (13) (x=7, R=n-Bu, Z=Et).

EXAMPLE 73 9-propyltetradecanoic Acid

[0224] Following General Procedure VIII use 1-bromopropane in step (c)(Z=CH₃(CH₂)₂₋) and use 1-bromopropane in step (f) (R═CH₃(CH₂)₂₋) toeventually obtain 2-propyl-1-octanol as compound (9). This is convertedto its bromide in step (I) and to its Grignard reagent in step (m).Following the sequence (n−1), (o), (p), (n−1), (o), (p), (n−1), (o), (p)(that is, three iterations of ethylene oxide) gives final Grignardreagent (12), x=7, R=n-Pr, Z=n-Pr which with CO₂ treatment gives9-propyltetradecanoic acid (13) (x=7, R=n-Pr, Z=n-Pr).

EXAMPLE 74 7-propyltetradecanoic Acid

[0225] Following General Procedure VIII use 1-bromopropane in step (c)(Z=CH₃(CH₂)₂₋) and use 1-bromopentane in step (f) (R═CH₃(CH₂)₄₋) toeventually obtain 2-propyl-1-nonanol as compound (9). This is convertedto its bromide in step (l) and to its Grignard reagent in step (m).Following the sequence (n−1), (o), (p), (n−1), (o), (p), (that is, twoiterations of ethylene oxide) gives final Grignard reagent (12), x=5,R=n-pentyl, Z=n-Pr which with CO₂ treatment gives 7-propyltetradecanoicacid (13) (x=5, R=n-pentyl, Z=n-Pr).

EXAMPLE 75 7-ethylpentadecanoic Acid

[0226] Following General Procedure VIII use ethyl bromide in step (c)(Z=CH₃CH₂-) and use 1-bromohexane in step (f) (R═CH₃(CH₂)₅₋) toeventually obtain 2-ethyl-1-decanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n−1), (o), (p), (n−1), (o), (p), (that is, twoiterations of ethylene oxide) gives final Grignard reagent (12), x=5,R=n-hexyl, Z=Et which with CO₂ treatment gives 7-ethylpentadecanoic acid(13) (x=5, R=n-hexyl, Z=Et).

EXAMPLE 76 5-propyldodecanoic Acid

[0227] Following General Procedure VIII use 1-bromopropane in step (c)(Z=CH₃(CH₂)₂₋) and use 1-bromopentane in step (f) (R═CH₃(CH₂)₄₋) toeventually obtain 2-propyl-1-nonanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n−1), (o), (p) gives final Grignard reagent(12), x=3, R=n-pentyl, Z=n-Pr which with CO₂ treatment gives5-propyldodecanoic acid (13) (x=3, R=n-pentyl, Z=n-Pr).

EXAMPLE 77 6-ethyltridecanoic Acid

[0228] Following General Procedure VIII use ethyl bromide in step (c)(Z=CH₃CH₂₋) and use 1-bromopentane in step (f) (R═CH₃(CH₂)₄₋) toeventually obtain 2-ethyl-1-nonanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n−1), (o), (p), (n−2), (o), (p) (that is, oneethylene oxide iteration and one formaldehyde iteration) gives finalGrignard reagent (12), x=4, R=n-pentyl, Z=Et which with CO₂ treatmentgives 6-ethyltridecanoic acid (13) (x=4, R=n-pentyl, Z=Et).

EXAMPLE 78 Sodium Soaps

[0229] 10 mmol of fatty acid is added to about 10.2 mmol of sodiumhydroxide predissolved in 100 ml of methanol. A little water mayoptionally be present. The methanol is evaporated to give the soap. Thesodium soap is made in this way for each one of the preceding fattyacids listed above.

EXAMPLE 79 Potassium Soaps

[0230] 10 mmol of fatty acid is added to about 10.2 mmol of potassiumhydroxide predissolved in 100 ml of methanol. A little water mayoptionally be present. The methanol is evaporated to give the soap. Thepotassium soap is made in this way for each one of the preceding fattyacids listed above.

EXAMPLE 80 Ammonium Soaps

[0231] 10 mmol of fatty acid is added to about 10.2 mmol of ammonia(used as concentrated aqueous reagent) predissolved in 100 ml ofmethanol. The solvent is evaporated to give the soap. The ammonium soapis made in this way for each one of the preceding fatty acids listedabove.

EXAMPLE 81 Calcium Soaps

[0232] Sodium Soap made as per Example 78 (10 mmol) is dissolved inwater and treated slowly with stirring with 5 mmol of Calcium Chlorideas a 10% aqueous solution.

[0233] The resulting slurry is filtered, washed and dried. The calciumsoap is made in this way for each one of the preceding fatty acidslisted above.

EXAMPLE 82 Magnesium Soaps

[0234] Sodium Soap made as per Example 78 (10 mmol) is dissolved inwater and treated slowly with stirring with 5 mmol of Magnesium Chlorideas a 10% aqueous solution.

[0235] The resulting slurry is filtered, washed and dried. The magnesiumsoap is made in this way for each one of the preceding fatty acidslisted above.

INDUSTRIAL APPLICABILITY

[0236] The compositions, e.g., the various novel fatty acids and saltsof the type herein can be used in all manner of compositions. Detergentcompositions of the invention may also contain additional detergentcomponents. The precise nature of these additional components, andlevels of incorporation thereof will depend on the physical form of thecleaning composition, and the precise nature of the cleaning operationfor which it is to be used. Cleaning compositions herein include, butare not limited to: granular, bar-form and liquid laundry detergents;liquid hand dishwashing compositions; liquid, gel and bar-form personalcleansing products; shampoos; dentifrices; hard surface cleaners, andthe like. Such compositions can contain a variety of conventionaldetersive ingredients.

[0237] The compositions, e.g., the various novel fatty acids and saltsof the type herein can be used in all manner of skin care compositions.The precise nature of these additional components, and levels ofincorporation thereof will depend on the physical form of the skin carecomposition, and the precise nature of the skin care operation for whichit is to be used.

[0238] The following listing of such ingredients is for the convenienceof the formulator, and not by way of limitation of the types ofingredients which can be used with the branched-chain surfactantsherein. The cleaning compositions of the invention preferably containone or more conventional detergent additives for example surfactants,builders, alkalinity system, organic polymeric compounds, sudssuppressors, soil suspension and anti-redeposition agents and corrosioninhibitors. The skin care compositions of the invention preferablycontain one or more conventional skin care additives, for example,fragrances, emollients, anti-acne actives, thickeners, structuringagents and skin conditioners.

[0239] Conventional Detergent Additives

[0240] Detersive Surfactants:

[0241] The detergent compositions according to the present inventionpreferably further comprise additional surfactants, herein also referredto as co-surfactants. It is to be understood that the branched-chainsurfactants prepared in the manner of the present invention may be usedsingly in cleaning compositions or in combination with other detersivesurfactants. Typically, fully-formulated cleaning compositions willcontain a mixture of surfactant types in order to obtain broad-scalecleaning performance over a variety of soils and stains and under avariety of usage conditions. One advantage of the branched-chainsurfactants herein is their ability to be readily formulated incombination with other known surfactant types.

[0242] A wide range of these co-surfactants can be used in the detergentcompositions of the present invention. A typical listing of anionic,nonionic, cationic, ampholytic and zwitterionic classes, and species ofthese co-surfactants, is given in U.S. Pat. No. 3,664,961 issued toNorris on May 23, 1972. Amphoteric surfactants are also described indetail in “Amphoteric Surfactants, Second Edition”, E. G. Lomax, Editor(published 1996, by Marcel Dekker, Inc.) McCutcheon's, Emulsifiers andDetergents, Annually published by M. C. Publishing Co., and SurfaceActive Agents and Detergents” (Vol. I and II by Schwartz, Perry andBerch). which are incorporated herein by reference.

[0243] The laundry detergent compositions of the present inventiontypically comprise from about 0.1% to about 50%, preferably from about0.5% to about 35%, more preferably 0.5% to about 30%, by weight ofco-surfactants. Selected co-surfactants are further identified asfollows.

[0244] Anionic Co-surfactants—Nonlimiting examples of anionicco-surfactants useful herein, typically at levels from about 0.1% toabout 50%, by weight, include the conventional C₁₁-C₁₈ alkyl benzenesulfonates (“LAS”) and primary, branched-chain and random C₁₀-C₂₀ alkylsulfates (“AS”), the C₁₀-C₁₈ secondary (2,3) alkyl sulfates of theformula CH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺) CH₃ and CH₃ (CH₂)_(y)(CHOSO₃ ⁻M⁺)CH₂CH₃ where x and (y+1) are integers of at least about 7, preferably atleast about 9, and M is a water-solubilizing cation, especially sodium,unsaturated sulfates such as oleyl sulfate, the C₁₀-C₁₈ alpha-sulfonatedfatty acid esters, the C₁₀-C₁₈ sulfated alkyl polyglycosides, theC₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”; especially EO 1-7 ethoxysulfates), and C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5ethoxycarboxylates). The C₁₂-C₁₈ betaines and sulfobetaines(“sultaines”), C₁₀-C₁₈ amine oxides, and the like, can also be includedin the overall compositions. C₁₀-C₂₀ conventional soaps may also beused. Other conventional useful anionic co-surfactants are listed instandard texts.

[0245] The alkyl alkoxy sulfate surfactants useful herein are preferablywater soluble salts or acids of the formula RO(A)_(m)SO₃M wherein R isan unsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄alkyl component, preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, morepreferably C₁₂-C₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxyunit, m is greater than zero, typically between about 0.5 and about 6,more preferably between about 0.5 and about 3, and M is H or a cationwhich can be, for example, a metal cation, ammonium orsubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulfates are contemplated herein.

[0246] The alkyl sulfate surfactants useful herein are preferably watersoluble salts or acids of the formula ROSO₃M wherein R preferably is aC₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having aC₁₀-C₁₈ alkyl component, more preferably a C₁₂-C₁₅ alkyl orhydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.sodium, potassium, lithium), or ammonium or substituted ammonium.

[0247] Other suitable anionic surfactants that can be used are alkylester sulfonate surfactants including linear esters of C₈-C₂₀ carboxylicacids (i.e., fatty acids) which are sulfonated with gaseous SO₃according to “The Journal of the American Oil Chemists Society”, 52(1975), pp. 323-329. Suitable starting materials would include naturalfatty substances as derived from tallow, palm oil, etc.

[0248] Other anionic co-surfactants useful for detersive purposes canalso be included in the laundry detergent compositions of the presentinvention. These can include salts of soap, C₈-C₂₂ primary of secondaryalkanesulfonates, C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylicacids prepared by sulfonation of the pyrolyzed product of alkaline earthmetal citrates, e.g., as described in British patent specification No.1,082,179, C₈-C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerolsulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxideether sulfates, paraffin sulfonates, alkyl phosphates, isethionates suchas the acyl isethionates, N-acyl taurates, alkyl succinamates andsulfosuccinates, monoesters of sulfosuccinates (especially saturated andunsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates(especially saturated and unsaturated C₆-C₁₂ diesters), sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), and alkylpolyethoxy carboxylates such as those of the formulaRO(CH₂CH₂O)_(k)—CH₂COO-M+ wherein R is a C₈-C₂₂ alkyl, k is an integerfrom 0 to 10, and M is a soluble salt-forming cation. Resin acids andhydrogenated resin acids are also suitable, such as rosin, hydrogenatedrosin, and resin acids and hydrogenated resin acids present in orderived from tall oil. A variety of such surfactants are also generallydisclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin,et al. at Column 23, line 58 through Column 29, line 23 (hereinincorporated by reference).

[0249] Another possible surfactant are the so-called Dianionics. Theseare surfactants which have at least two anionic groups present on thesurfactant molecule. Some suitable dianionic surfactants are furtherdescribed in copending U.S. Serial No. 60/020,503 (Docket No. 6160P),60/020,772 (Docket No. 6161P), 60/020,928 (Docket No. 6158P), 60/020,832(Docket No. 6159P) and 60/020,773 (Docket No. 6162P) all filed on Jun.28, 1996, and No. 60/023,539 (Docket No. 6192P), 60/023,493 (Docket No.6194P), 60/023,540 (Docket No. 6193P) and 60/023,527 (Docket No. 6195P)filed on Aug. 8, 1996, the disclosures of which are incorporated hereinby reference. Other conventional useful surfactants are listed instandard texts.

[0250] Additionally, the surfactant may be a branched alkyl sulfate,branched alkyl alkoxylate, branched alkyl alkoxylate sulfate or midchain branched alkyl aryl sulfonate. These Surfactants are furtherdescribed in copending U.S. Patent applications No. 60/053,319 Attorneydocket No 6766P filed on July 21st, 1997, No. 60/053,318, Attorneydocket No 6767P filed on July 21st, 1997, No. 60/053,321, Attorneydocket No 6768P filed on July 21st, 1997, No. 60/053,209, Attorneydocket No 6769P filed on July 21st, 1997, No. 60/053,328, Attorneydocket No 6770P filed on July 21st, 1997, No. 60/053,186, Attorneydocket No 6771P filed on July 21st, 1997, No. 60/061,971, Attorneydocket No 6881P Oct. 14, 1997, No. 60/061,975, Attorney docket No 6882POct. 14, 1997, No. 60/062,086, Attorney docket No 6883P Oct. 14, 1997,No. 60/061,916, Attorney docket No 6884P Oct. 14, 1997, No. 60/061,970,Attorney docket No 6885P Oct. 14, 1997, No. 60/062,407, Attorney docketNo 6886P Oct. 14, 1997,. Other suitable mid-chain branched surfactantscan be found in U.S. Patent applications Serial Nos. 60/032,035 (DocketNo. 6401P), 60/031,845 (Docket No. 6402P), 60/031,916 (Docket No.6403P), 60/031,917 (Docket No. 6404P), 60/031,761 (Docket No. 6405P),60/031,762 (Docket No. 6406P) and 60/031,844 (Docket No. 6409P).Mixtures of these branched surfactants with conventional linearsurfactants are also suitable for use in the present compositions.

[0251] Nonionic Co-surfactants—Nonlimiting examples of nonionicco-surfactants useful herein typically at levels from about 0.1% toabout 50%, by weight include the alkoxylated alcohols (AE's) and alkylphenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides(APG's), C₁₀-C₁₈ glycerol ethers, and the like.

[0252] More specifically, the condensation products of primary andsecondary aliphatic alcohols with from about 1 to about 25 moles ofethylene oxide (AE) are suitable for use as the nonionic surfactant inthe present invention. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from about 8 to about 22 carbon atoms. Preferred are thecondensation products of alcohols having an alkyl group containing fromabout 8 to about 20 carbon atoms, with from about 1 to about 10 moles ofethylene oxide per mole of alcohol. Especially preferred nonionicsurfactants of this type are the C₉-C₁₅ primary alcohol ethoxylatescontaining 3-12 moles of ethylene oxide per mole of alcohol,particularly the C₁₂-C₁₅ primary alcohols containing 5-10 moles ofethylene oxide per mole of alcohol.

[0253] Examples of commercially available nonionic surfactants of thistype include: Tergitol™ 15-S-9 (the condensation product of C₁₁-C₁₅linear alcohol with 9 moles ethylene oxide) and Tergitol™ 24-L-6 NMW(the condensation product of C₁₂-C₁₄ primary alcohol with 6 molesethylene oxide with a narrow molecular weight distribution), bothmarketed by Union Carbide Corporation; Neodol™ 45-9 (the condensationproduct of C₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide),Neodol™ 23-3 (the condensation product of C₁₂-C₁₃ linear alcohol with 3moles of ethylene oxide), Neodol™ 45-7 (the condensation product ofC₁₄-C₁₅ linear alcohol with 7 moles of ethylene oxide) and Neodol™ 45-5(the condensation product of C₁₄-C₁₅ linear alcohol with 5 moles ofethylene oxide) marketed by Shell Chemical Company; Kyro™ EOB (thecondensation product of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide),marketed by The Procter & Gamble Company; and Genapol LA 030 or 050 (thecondensation product of C₁₂-C₁₄ alcohol with 3 or 5 moles of ethyleneoxide) marketed by Hoechst. The preferred range of HLB in these AEnonionic surfactants is from 8-17 and most preferred from 8-14.Condensates with propylene oxide and butylene oxides may also be used.

[0254] Another class of preferred nonionic co-surfactants for use hereinare the polyhydroxy fatty acid amide surfactants of the formula.

[0255] wherein R¹ is H, or C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl orC₁₅₋₁₇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction. Typical examplesinclude the C₁₂-C₁₈ and C₁₂-C₁₄ N-methylglucamides. See U.S. Pat. No.5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can alsobe used; see U.S. Pat. No. 5,489,393.

[0256] Also useful as a nonionic co-surfactant in the present inventionare the alkylpolysaccharides such as those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986, and EP-Patents B 0 070 077, 0075 996 and 0 094 118.

[0257] Polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols are also suitable for use as the nonionic surfactant ofthe surfactant systems of the present invention, with the polyethyleneoxide condensates being preferred. These compounds include thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to about 14 carbon atoms, preferably from about 8 to about14 carbon atoms, in either a straight-chain or branched-chainconfiguration with the alkylene oxide. In a preferred embodiment, theethylene oxide is present in an amount equal to from about 2 to about 25moles of ethylene oxide per mole of alkyl phenol. Commercially availablenonionic surfactants of this type include Igepal™ CO-630, marketed bythe GAF Corporation; and Triton™ X-45, X-114, X-100 and X-102, allmarketed by the Rohm & Haas Company. These surfactants are commonlyreferred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

[0258] Examples of other suitable nonionic surfactants are thecommercially-available Pluronic™ surfactants, marketed by BASF, thecommercially available Tetronic™ compounds, marketed by BASF.

[0259] Also preferred nonionics are amine oxide surfactants. Thecompositions of the present invention may comprise amine oxide inaccordance with the general formula I:

R¹(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂·qH₂O  (I).

[0260] In general, it can be seen that the structure (I) provides onelong-chain moiety R1(EO)_(x)(PO)_(y)(BO)_(z) and two short chainmoieties, CH₂R′. R′ is preferably selected from hydrogen, methyl and—CH₂OH. In general R¹ is a primary or branched hydrocarbyl moiety whichcan be saturated or unsaturated, preferably, R¹ is a primary alkylmoiety. When x+y+z=0, R¹ is a hydrocarbyl moiety having chainlength offrom about 8 to about 18. When x+y+z is different from 0, R¹ may besomewhat longer, having a chainlength in the range C₁₂-C₂₄. The generalformula also encompasses amine oxides wherein x+y+z=0, R₁═C₈-C₁₈, R′=Hand q=0-2, preferably 2. These amine oxides are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamineoxide and their hydrates, especially the dihydrates as disclosed in U.S.Pat. Nos. 5,075,501 and 5,071,594, incorporated herein by reference.

[0261] Highly preferred amine oxides herein are solutions at ambienttemperature. Amine oxides suitable for use herein are made commerciallyby a number of suppliers, including Akzo Chemie, Ethyl Corp., andProcter & Gamble. See McCutcheon's compilation and Kirk-Othmer reviewarticle for alternate amine oxide manufacturers.

[0262] Whereas in certain of the preferred embodiments R′ is H, there issome latitude with respect to having R′ slightly larger than H.Specifically, the invention further encompasses embodiments wherein R′is CH₂OH, such as hexadecylbis(2-hydroxyethyl)amine oxide,tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amineoxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamineoxide dihydrate.

[0263] Cationic Co-surfactants—Nonlimiting examples of cationicco-surfactants useful herein typically at levels from about 0.1% toabout 50%, by weight include the choline ester-type quats andalkoxylated quaternary ammonium (AQA) surfactant compounds, and thelike.

[0264] Cationic co-surfactants useful as a component of the surfactantsystem is a cationic choline ester-type quat surfactant which arepreferably water dispersible compounds having surfactant properties andcomprise at least one ester (i.e. —COO—) linkage and at least onecationically charged group. Suitable cationic ester surfactants,including choline ester surfactants, have for example been disclosed inU.S. Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

[0265] Preferred cationic ester surfactants are those having theformula:

[0266] wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl oralkaryl chain or M⁻.N⁺(R₆R₇R₈)(CH₂)_(s); X and Y, independently, areselected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO,OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO,OCONH or NHCOO group; R₂, R₃, R₄, R₆, R₇ and R₈ are independentlyselected from the group consisting of alkyl, alkenyl, hydroxyalkyl,hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; andR₅ is independently H or a C₁-C₃ alkyl group; wherein the values of m,n, s and t independently lie in the range of from 0 to 8, the value of blies in the range from 0 to 20, and the values of a, u and vindependently are either 0 or I with the proviso that at least one of uor v must be 1; and wherein M is a counter anion.

[0267] Preferably R₂, R₃ and R₄ are independently selected from CH₃ and—CH₂CH₂OH.

[0268] Preferably M is selected from the group consisting of halide,methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate,chloride, bromide or iodide.

[0269] Preferred water dispersible cationic ester surfactants are thecholine esters having the formula:

[0270] wherein R₁ is a C₁₁-C₁₉ linear or branched alkyl chain.

[0271] Other suitable cationic ester surfactants have the structuralformulas below, wherein d may be from 0 to 20.

[0272] In a preferred aspect these cationic ester surfactant arehydrolysable under the conditions of a laundry wash method.

[0273] Cationic co-surfactants useful herein also include alkoxylatedquaternary ammonium (AQA) surfactant compounds (referred to hereinafteras “AQA compounds”) having the formula:

[0274] wherein R¹ is a linear or branched alkyl or alkenyl moietycontaining from about 8 to about 18 carbon atoms, preferably 10 to about16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;R² is an alkyl group containing from one to three carbon atoms,preferably methyl; R³ and R⁴ can vary independently and are selectedfrom hydrogen (preferred), methyl and ethyl; X⁻ is an anion such aschloride, bromide, methylsulfate, sulfate, or the like, sufficient toprovide electrical neutrality. A and A′ can vary independently and areeach selected from C₁-C₄ alkoxy, especially ethoxy (i.e., —CH₂CH₂O—),propoxy, butoxy and mixed ethoxy/propoxy; p is from 0 to about 30,preferably I to about 4 and q is from 0 to about 30, preferably I toabout 4, and most preferably to about 4; preferably both p and q are 1.See also: EP 2,084, published May 30, 1979, by The Procter & GambleCompany, which describes cationic co-surfactants of this type which arealso useful herein.

[0275] AQA compounds wherein the hydrocarbyl substituent R¹ is C₈-C₁₁,especially C₁₀, enhance the rate of dissolution of laundry granules,especially under cold water conditions, as compared with the higherchain length materials. Accordingly, the C₈-C₁₁ AQA surfactants may bepreferred by some formulators. The levels of the AQA surfactants used toprepare finished laundry detergent compositions can range from about0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.Designation R¹ R² ApR³ A′qR⁴ AQA-1 C₁₂-C₁₄ CH₃ EO EO (also referred toas Coco Methyl EO2) AQA-2 C₁₂-C₁₆ CH₃ (EO)₂ EO AQA-3 C₁₂-C₁₄ CH₃ (EO)₂(EO)₂ (Coco Methyl EO4) AQA-4 C₁₂ CH₃ EO EO AQA-5 C₁₂-C₁₄ CH₃ (EO)₂(EO)₃ AQA-6 C₁₂-C₁₄ CH₃ (EO)₂ (EO)₃ AQA-7  C₈-C₁₈ CH₃ (EO)₃ (EO)₂ AQA-8C₁₂-C₁₄ CH₃ (EO)₄ (EO)₄ AQA-9 C₁₂-C₁₄ C₂H₅ (EO)₃ (EO)₃ AQA-10 C₁₂-C₁₈C₃H₇ (EO)₃ (EO)₄ AQA-11 C₁₂-C₁₈ CH₃ (propoxy) (EO)₃ AQA-12 C₁₀-C₁₈ C₂H₅(iso-propoxy)₂ (EO)₃ AQA-13 C₁₀-C₁₈ CH₃ (EO/PO)₂ (EO)₃ AQA-14  C₈-C₁₈CH₃ (EO)₁₅* (EO)₁₅* AQA-15 C₁₀ CH₃ EO EO AQA-16  C₈-C₁₂ CH₃ EO EO AQA-17 C₉-C₁₁ CH₃ —EO 3.5 Avg.— AQA-18 C₁₂ CH₃ —EO 3.5 Avg.— AQA-19  C₈-C₁₄CH₃ (EO)₁₀ (EO)₁₀ AQA-20 C₁₀ C₂H₅ (EO)₂ (EO)₃ AQA-21 C₁₂-C₁₄ C₂H₅ (EO)₅(EO)₃ AQA-22 C₁₂-C₁₈ C₃H₇ Bu (EO)₂

[0276] The preferred bis-ethoxylated cationic surfactants herein areavailable under the trade name ETHOQUAD from Akzo Nobel ChemicalsCompany.

[0277] Highly preferred bis-AQA compounds for use herein are of theformula

[0278] wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof,preferably C₁₀, C₁₂, C₁₄ alkyl and mixtures thereof, and X is anyconvenient anion to provide charge balance, preferably chloride. Withreference to the general AQA structure noted above, since in a preferredcompound R¹ is derived from coconut (C₁₂-C₁₄ alkyl) fraction fattyacids, R² is methyl and ApR³ and A′qR⁴ are each monoethoxy, thispreferred type of compound is referred to herein as “CocoMeEO2” or“AQA-1” in the above list.

[0279] Other preferred AQA compounds herein include compounds of theformula:

[0280] wherein R¹ is C₁₀-C₁₈ hydrocarbyl, preferably C₁₀-C₁₄ alkyl,independently p is I to about 3 and q is 1 to about 3, R² is C₁-C₃alkyl, preferably methyl, and X is an anion, especially chloride.

[0281] Other compounds of the foregoing type include those wherein theethoxy (CH₂CH₂O) units (EO) are replaced by butoxy (Bu), isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

[0282] The following illustrates various other adjunct ingredients whichmay be used in the compositions of this invention, but is not intendedto be limiting thereof. While the combination of the mid-chain branchedprimary alkyl surfactants with such adjunct compositional ingredientscan be provided as finished products in the form of liquids, gels, bars,or the like using conventional techniques, the manufacture of thegranular laundry detergents herein requires some special processingtechniques in order to achieve optimal performance. Accordingly, themanufacture of laundry granules will be described hereinafter separatelyin the Granules Manufacture section (below), for the convenience of theformulator.

[0283] Additional cationic co-surfactants are described, for example, inthe “Surfactant Science Series, Volume 4, Cationic Surfactants” or inthe “Industrial Surfactants Handbook”. Classes of useful cationicsurfactants described in these references include amide quats (i.e.,Lexquat AMG & Schercoquat CAS), glycidyl ether quats (i.e., Cyostat609), hydroxyalkyl quats (i.e., Dehyquart E), alkoxypropyl quats (i.e.,Tomah Q-17-2), polypropoxy quats (Emcol CC-9), cyclic alkylammoniumcompounds (i.e., pyridinium or imidazolinium quats), and/or benzalkoniumquats.

[0284] Detersive Enzymes—Enzymes are preferably included in the presentdetergent compositions for a variety of purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains fromsubstrates, for the prevention of refugee dye transfer in fabriclaundering, and for fabric restoration. Recent enzyme disclosures indetergents useful herein include bleach/amylase/protease combinations(EP 755,999 A; EP 756,001 A; EP 756,000 A); chondriotinase (EP 747,469A); protease variants (WO 96/28566 A; WO 96/28557 A; WO 96/28556 A; WO96/25489 A); xylanase (EP 709,452 A); keratinase (EP 747,470 A); lipase(GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154A); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A);thermitase (WO 96/28558 A). More generally, suitable enzymes includeproteases, amylases, lipases, cellulases, peroxidases, xylanases,keratinases, chondriotinases; thermitases, cutinases and mixturesthereof of any suitable origin, such as vegetable, animal, bacterial,fungal and yeast origin. Preferred selections are influenced by factorssuch as pH-activity and/or stability optima, thermostability, andstability to active detergents, builders and the like. In this respectbacterial or fungal enzymes are preferred, such as bacterial amylasesand proteases, and fungal cellulases. Suitable enzymes are alsodescribed in U.S. Pat. Nos. 5,677,272, 5,679,630, 5,703,027, 5,703,034,5,705,464, 5,707,950, 5,707,951, 5,710,115, 5,710,116, 5,710,118,5,710,119 and 5,721,202.

[0285] “Detersive enzyme”, as used herein, means any enzyme having acleaning, stain removing or otherwise beneficial effect in a laundry,hard surface cleaning or personal care detergent composition. Preferreddetersive enzymes are hydrolases such as proteases, amylases andlipases. Preferred enzymes for laundry purposes include, but are notlimited to, proteases, cellulases, lipases and peroxidases. Highlypreferred are amylases and/or proteases, including both currentcommercially available types and improved types which, though more andmore bleach compatible though successive improvements, have a remainingdegree of bleach deactivation susceptibility.

[0286] Enzymes are normally incorporated into detergent or detergentadditive compositions at levels sufficient to provide a“cleaning-effective amount”. The term “cleaning effective amount” refersto any amount capable of producing a cleaning, stain removal, soilremoval, whitening, deodorizing, or freshness improving effect onsubstrates such as fabrics, dishware and the like. In practical termsfor current commercial preparations, typical amounts are up to about 5mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gramof the detergent composition. Stated otherwise, the compositions hereinwill typically comprise from 0.001% to 5%, preferably 0.01%-1% by weightof a commercial enzyme preparation. Protease enzymes are usually presentin such commercial preparations at levels sufficient to provide from0.005 to 0.1 Anson units (AU) of activity per gram of composition. Forcertain detergents it may be desirable to increase the active enzymecontent of the commercial preparation in order to minimize the totalamount of non-catalytically active materials and thereby improvespotting/filming or other end-results. Higher active levels may also bedesirable in highly concentrated detergent formulations.

[0287] Suitable examples of proteases are the subtilisins which areobtained from particular strains of B. subtilis and B. licheniformis.One suitable protease is obtained from a strain of Bacillus, havingmaximum activity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble. When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

[0288] In more detail, an especially preferred protease, referred to as“Protease D” is a carbonyl hydrolase variant having an amino acidsequence not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalentto position +76, preferably also in combination with one or more aminoacid residue positions equivalent to those selected from the groupconsisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126,+128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218,+222, +260, +265, and/or +274 according to the numbering of Bacillusamyloliquefaciens subtilisin, as described in WO 95/10615 published Apr.20, 1995 by Genencor International.

[0289] Useful proteases are also described in PCT publications: WO95/30010 published Nov. 9, 1995 by The Procter & Gamble Company; WO95/30011 published Nov. 9, 1995 by The Procter & Gamble Company;WO-95/29979 published Nov. 9, 1995 by The Procter & Gamble Company.

[0290] Amylases suitable herein include, for example, α-amylasesdescribed in GB 1,296,839 to Novo; RAPIDASE®, InternationalBio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo isespecially useful. Engineering of enzymes for improved stability, e.g.,oxidative stability, is known. See, for example J. Biological Chem.,Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferredembodiments of the present compositions can make use of amylases havingimproved stability in detergents, especially improved oxidativestability as measured against a reference-point of TERMAMYL® incommercial use in 1993. These preferred amylases herein share thecharacteristic of being “stability-enhanced” amylases, characterized, ata minimum, by a measurable improvement in one or more of: oxidativestability, e.g., to hydrogen peroxide/tetraacetylethylenediamine inbuffered solution at pH 9-10; thermal stability, e.g., at common washtemperatures such as about 60° C.; or alkaline stability, e.g., at a pHfrom about 8 to about 11, measured versus the above-identifiedreference-point amylase. Stability can be measured using any of theart-disclosed technical tests. See, for example, references disclosed inWO 9402597. Stability-enhanced amylases can be obtained from Novo orfrom Genencor International. One class of highly preferred amylasesherein have the commonality of being derived using site-directedmutagenesis from one or more of the Bacillus amylases, especially theBacillus α-amylases, regardless of whether one, two or multiple amylasestrains are the immediate precursors. Oxidative stability-enhancedamylases vs. the above-identified reference amylase are preferred foruse, especially in bleaching, more preferably oxygen bleaching, asdistinct from chlorine bleaching, detergent compositions herein. Suchpreferred amylases include (a) an amylase according to the hereinbeforeincorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by amutant in which substitution is made, using alanine or threonine,preferably threonine, of the methionine residue located in position 197of the B. licheniformis alpha-amylase, known as TERMAMYL®, or thehomologous position variation of a similar parent amylase, such as B.amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th American Chemical Society National Meeting, Mar. 13-17, 1994, byC. Mitchinson. Therein it was noted that bleaches in automaticdishwashing detergents inactivate alpha-amylases but that improvedoxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the mostlikely residue to be modified. Met was substituted, one at a time, inpositions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants,particularly important being M197L and M197T with the M197T variantbeing the most stable expressed variant. Stability was measured inCASCADE® and SUNLIGHT®; (c) particularly preferred amylases hereininclude amylase variants having additional modification in the immediateparent as described in WO 9510603 A and are available from the assignee,Novo, as DURAMYL®. Other particularly preferred oxidative stabilityenhanced amylase include those described in WO 9418314 to GenencorInternational and WO 9402597 to Novo. Any other oxidativestability-enhanced amylase can be used, for example as derived bysite-directed mutagenesis from known chimeric, hybrid or simple mutantparent forms of available amylases. Other preferred enzyme modificationsare accessible. See WO 9509909 A to Novo.

[0291] Other amylase enzymes include those described in WO 95/26397 andin co-pending application by Novo Nordisk PCT/DK96/00056. Specificamylase enzymes for use in the detergent compositions of the presentinvention include α-amylases characterized by having a specific activityat least 25% higher than the specific activity of Termamyl® at atemperature range of 25° C. to 55° C. and at a pH value in the range of8 to 10, measured by the Phadebas® α-amylase activity assay. (SuchPhadebas® α-amylase activity assay is described at pages 9-10, WO95/26397.) Also included herein are α-amylases which are at least 80%homologous with the amino acid sequences shown in the SEQ ID listings inthe references. These enzymes are preferably incorporated into laundrydetergent compositions at a level from 0.00018% to 0.060% pure enzyme byweight of the total composition, more preferably from 0.00024% to 0.048%pure enzyme by weight of the total composition.

[0292] Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME®(Novo) are especially useful. See also WO 9117243 to Novo.

[0293] Suitable lipase enzymes for detergent usage include thoseproduced by microorganisms of the Pseudomonas group, such as Pseudomonasstutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases inJapanese Patent Application 53,20487, laid open Feb. 24, 1978. Thislipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,under the trade name Lipase P “Amano,” or “Amano-P.” Other suitablecommercial lipases include Amano-CES, lipases ex Chromobacter viscosum,e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo JozoCo., Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein. Lipase and amylase variants stabilizedagainst peroxidase enzymes are described in WO 9414951 A to Novo. Seealso WO 9205249 and RD 94359044.

[0294] Cutinase enzymes suitable for use herein are described in WO8809367 A to Genencor.

[0295] Peroxidase enzymes may be used in combination with oxygensources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for“solution bleaching” or prevention of transfer of dyes or pigmentsremoved from substrates during the wash to other substrates present inthe wash solution. Known peroxidases include horseradish peroxidase,ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

[0296] A range of enzyme materials and means for their incorporationinto synthetic detergent compositions is also disclosed in WO 9307263 Aand WO 9307260 A to Genencor International, WO 8908694 A to Novo, andU.S. Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes arefurther disclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18,1978, and in U.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzymematerials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al, Apr. 14, 1981. Enzymes for use in detergents canbe stabilized by various techniques. Enzyme stabilization techniques aredisclosed and exemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971,Gedge et al, EP 199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzymestabilization systems are also described, for example, in U.S. Pat. No.3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases andcellulases, is described in WO 9401532 A to Novo.

[0297] Builders—Detergent builders are preferably included in thecompositions herein, for example to assist in controlling mineral,especially Ca and/or Mg, hardness in wash water or to assist in theremoval and/or suspension of particulate soils from surfaces andsometimes to provide alkalinity and/or buffering action. In solidformulations, builders sometimes serve as absorbents for surfactants.Alternately, certain compositions can be formulated with completelywater-soluble builders, whether organic or inorganic, depending on theintended use.

[0298] Suitable silicate builders include water-soluble and hydroussolid types and including those having chain-, layer-, orthree-dimensional-structure as well as amorphous-solid silicates orother types, for example especially adapted for use innon-structured-liquid detergents. Preferred are alkali metal silicates,particularly those liquids and solids having a SiO₂:Na₂O ratio in therange 1.6:1 to 3.2:1, including solid hydrous 2-ratio silicates marketedby PQ Corp. under the tradename BRITESIL®, e.g., BRITESIL H₂O; andlayered silicates, e.g., those described in U.S. Pat. No. 4,664,839, May12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated “SKS-6”, is acrystalline layered aluminum-free δ-Na₂SiO₅ morphology silicate marketedby Hoechst and is preferred especially in granular laundry compositions.See preparative methods in German DE-A-3,417,649 and DE-A-3,742,043.Other layered silicates, such as those having the general formulaNaMSi_(x)O_(2x+1)·yH₂O wherein M is sodium or hydrogen, x is a numberfrom 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably0, can also or alternately be used herein. Layered silicates fromHoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the α, β and γlayer-silicate forms. Other silicates may also be useful, such asmagnesium silicate, which can serve as a crisping agent in granules, asa stabilizing agent for bleaches, and as a component of suds controlsystems.

[0299] Also suitable for use herein are synthesized crystalline ionexchange materials or hydrates thereof having chain structure and acomposition represented by the following general formula in an anhydrideform: xM₂O ySiO₂.zM′O wherein M is Na and/or K, M′ is Ca and/or Mg; y/xis 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. Pat. No.5,427,711, Sakaguchi et al, Jun. 27, 1995.

[0300] Aluminosilicate builders, such as zeolites, are especially usefulin granular detergents, but can also be incorporated in liquids, pastesor gels. Suitable for the present purposes are those having empiricalformula: [M_(z)(AlO₂)_(z)(SiO₂)_(v)] xH₂O wherein z and v are integersof at least 6, the molar ratio of z to v is in the range from 1.0 to0.5, and x is an integer from 15 to 264. Aluminosilicates can becrystalline or amorphous, naturally-occurring or synthetically derived.An aluminosilicate production method is in U.S. Pat. No. 3,985,669,Krummel, et al, Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials are available as Zeolite A,Zeolite P (B), Zeolite X and, to whatever extent this differs fromZeolite P, the so-called Zeolite MAP. Natural types, includingclinoptilolite, may be used. Zeolite A has the formula:Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O wherein x is from 20 to 30, especially 27.Dehydrated zeolites (x=0-10) may also be used. Preferably, thealuminosilicate has a particle size of 0.1-10 microns in diameter.

[0301] Builder level can vary widely depending upon end use and physicalform of the composition. Built detergents typically comprise at leastabout 1% builder. Liquid formulations typically comprise about 5% toabout 50%, more typically 5% to 35% of builder. Granular formulationstypically comprise from about 10% to about 80%, more typically 15% to50% builder by weight of the detergent composition. Lower or higherlevels of builders are not excluded. For example, certain detergentadditive or high-surfactant formulations can be unbuilt.

[0302] Suitable builders herein can be selected from the groupconsisting of phosphates and polyphosphates, especially the sodiumsalts; carbonates, bicarbonates, sesquicarbonates and carbonate mineralsother than sodium carbonate or sesquicarbonate; organic mono-, di-,tri-, and tetracarboxylates especially water-soluble nonsurfactantcarboxylates in acid, sodium, potassium or alkanolammonium salt form, aswell as oligomeric or water-soluble low molecular weight polymercarboxylates including aliphatic and aromatic types; and phytic acid.These may be complemented by borates, e.g., for ph-buffering purposes,or by sulfates, especially sodium sulfate and any other fillers orcarriers which may be important to the engineering of stable surfactantand/or builder-containing detergent compositions.

[0303] Builder mixtures, sometimes termed “builder systems” can be usedand typically comprise two or more conventional builders, optionallycomplemented by chelants, pH-buffers or fillers, though these lattermaterials are generally accounted for separately when describingquantities of materials herein. In terms of relative quantities ofsurfactant and builder in the present detergents, preferred buildersystems are typically formulated at a weight ratio of surfactant tobuilder of from about 60:1 to about 1:80. Certain preferred laundrydetergents have said ratio in the range 0.90:1.0 to 4.0:1.0, morepreferably from 0.95:1.0 to 3.0:1.0.

[0304] P-containing detergent builders often preferred where permittedby legislation include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates exemplified by thetripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; andphosphonates.

[0305] Suitable carbonate builders include alkaline earth and alkalimetal carbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973, although sodium bicarbonate, sodiumcarbonate, sodium sesquicarbonate, and other carbonate minerals such astrona or any convenient multiple salts of sodium carbonate and calciumcarbonate such as those having the composition 2Na₂CO₃.CaCO₃ whenanhydrous, and even calcium carbonates including calcite, aragonite andvaterite, especially forms having high surface areas relative to compactcalcite may be useful, for example as seeds or for use in syntheticdetergent bars.

[0306] Suitable “organic detergent builders”, as described herein foruse with the alkylarylsulfonate surfactant system includepolycarboxylate compounds, including water-soluble nonsurfactantdicarboxylates and tricarboxylates. More typically builderpolycarboxylates have a plurality of carboxylate groups, preferably atleast 3 carboxylates. Carboxylate builders can be formulated in acid,partially neutral, neutral or overbased form. When in salt form, alkalimetals, such as sodium, potassium, and lithium, or alkanolammonium saltsare preferred. Polycarboxylate builders include the etherpolycarboxylates, such as oxydisuccinate, see Berg, U.S. Pat. No.3,128,287, Apr. 7, 1964, and Lamberti et al, U.S. Pat. No. 3,635,830,Jan. 18, 1972; “TMS/TDS” builders of U.S. Pat. No. 4,663,071, Bush etal, May 5, 1987; and other ether carboxylates including cyclic andalicyclic compounds, such as those described in U.S. Pat. Nos.3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

[0307] Other suitable organic detergent builders are the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid; carboxymethyloxysuccinic acid; the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid; as well asmellitic acid, succinic acid, polymaleic acid, benzene1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and solublesalts thereof.

[0308] Citrates, e.g., citric acid and soluble salts thereof areimportant carboxylate builders e.g., for heavy duty liquid detergents,due to availability from renewable resources and biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicates. Oxydisuccinates arealso especially useful in such compositions and combinations.

[0309] Where permitted, and especially in the formulation of bars usedfor hand-laundering operations, alkali metal phosphates such as sodiumtripolyphosphates, sodium pyrophosphate and sodium orthophosphate can beused. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonateand other known phosphonates, e.g., those of U.S. Pat. Nos. 3,159,581;3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and mayhave desirable antiscaling properties.

[0310] Certain detersive surfactants or their short-chain homologuesalso have a builder action. For unambiguous formula accounting purposes,when they have surfactant capability, these materials are summed up asdetersive surfactants. Preferred types for builder functionality areillustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the relatedcompounds disclosed in U.S. Pat. No. 4,566,984, Bush, Jan. 28, 1986.Succinic acid builders include the C₅-C₂₀ alkyl and alkenyl succinicacids and salts thereof. Succinate builders also include:laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Lauryl-succinates are described in European Patent Application86200690.5/0,200,263, published Nov. 5, 1986. Fatty acids, e.g., C₁₂-C₁₈monocarboxylic acids, can also be incorporated into the compositions assurfactant/builder materials alone or in combination with theaforementioned builders, especially citrate and/or the succinatebuilders, to provide additional builder activity. Other suitablepolycarboxylates are disclosed in U.S. Pat. No. 4,144,226, Crutchfieldet al, Mar. 13, 1979 and in U.S. Pat. No. 3,308,067, Diehl, Mar. 7,1967. See also Diehl, U.S. Pat. No. 3,723,322.

[0311] Other types of inorganic builder materials which can be used havethe formula (M_(x))_(i) Ca_(y) (CO₃)_(z) wherein x and i are integersfrom 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to25, M_(i) are cations, at least one of which is a water-soluble, and theequation Σ_(i)=1-15(x_(i) multiplied by the valence of M_(i))+2y=2z issatisfied such that the formula has a neutral or “balanced” charge.These builders are referred to herein as “Mineral Builders”, examples ofthese builders, their use and preparation can be found in U.S. Pat. No.5,707,959. Another suitable class of inorganic builders are theMagnesiosilicates, see WO97/0179.

[0312] Bleaching Agents—Preferred compositions of the present inventioncomprise, as part or all of the laundry or cleaning adjunct materials, ableaching agent. Oxygen bleaching agents useful in the present inventioncan be any of the oxidizing agents known for laundry, hard surfacecleaning, automatic dishwashing or denture cleaning purposes. Oxygenbleaches or mixtures thereof are preferred, though other oxidantbleaches, such as oxygen, an enzymatic hydrogen peroxide producingsystem, or hypohalites such as chlorine bleaches like hypochlorite, mayalso be used.

[0313] Common oxygen bleaches of the peroxygen type include hydrogenperoxide, inorganic peroxohydrates, organic peroxohydrates and theorganic peroxyacids, including hydrophilic and hydrophobic mono- ordi-peroxyacids. These can be peroxycarboxylic acids, peroxyimidic acids,amidoperoxycarboxylic acids, or their salts including the calcium,magnesium, or mixed-cation salts. Peracids of various kinds can be usedboth in free form and as precursors known as “bleach activators” or“bleach promoters” which, when combined with a source of hydrogenperoxide, perhydrolyze to release the corresponding peracid.

[0314] Also useful herein as oxygen bleaches are the inorganic peroxidessuch as Na₂O₂, superoxides such as KO₂, organic hydroperoxides such ascumene hydroperoxide and t-butyl hydroperoxide, and the inorganicperoxoacids and their salts such as the peroxosulfuric acid salts,especially the potassium salts of peroxodisulfuric acid and, morepreferably, of peroxomonosulfuric acid including the commercialtriple-salt form sold as OXONE by DuPont and also any equivalentcommercially available forms such as CUROX from Akzo or CAROAT fromDegussa. Certain organic peroxides, such as dibenzoyl peroxide, may beuseful, especially as additives rather than as primary oxygen bleach.

[0315] Mixed oxygen bleach systems are generally useful, as are mixturesof any oxygen bleaches with the known bleach activators, organiccatalysts, enzymatic catalysts and mixtures thereof; moreover suchmixtures may further include brighteners, photobleaches and dye transferinhibitors of types well-known in the art.

[0316] Preferred oxygen bleaches, as noted, include the peroxohydrates,sometimes known as peroxyhydrates or peroxohydrates. These are organicor, more commonly, inorganic salts capable of releasing hydrogenperoxide readily. Peroxohydrates are the most common examples of“hydrogen peroxide source” materials and include the perborates,percarbonates, perphosphates, and persilicates. Suitable peroxohydratesinclude sodium carbonate peroxyhydrate and equivalent commercial“percarbonate” bleaches, and any of the so-called sodium perboratehydrates, the “tetrahydrate” and “monohydrate” being preferred; thoughsodium pyrophosphate peroxyhydrate can be used. Many such peroxohydratesare available in processed forms with coatings, such as of silicateand/or borate and/or waxy materials and/or surfactants, or have particlegeometries, such as compact spheres, which improve storage stability. Byway of organic peroxohydrates, urea peroxyhydrate can also be usefulherein.

[0317] Percarbonate bleach includes, for example, dry particles havingan average particle size in the range from about 500 micrometers toabout 1,000 micrometers, not more than about 10% by weight of saidparticles being smaller than about 200 micrometers and not more thanabout 10% by weight of said particles being larger than about 1,250micrometers. Percarbonates and perborates are widely available incommerce, for example from FMC, Solvay and Tokai Denka.

[0318] Organic percarboxylic acids useful herein as the oxygen bleachinclude magnesium monoperoxyphthalate hexahydrate, available fromInterox, m-chloro perbenzoic acid and its salts,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid andtheir salts. Such bleaches are disclosed in U.S. Pat. No. 4,483,781,U.S. Pat. Appl. 740,446, Burns et al, filed Jun. 3, 1985, EP-A 133,354,published Feb. 20, 1985, and U.S. Pat. No. 4,412,934. Organicpercarboxylic acids usable herein include those containing one, two ormore peroxy groups, and can be aliphatic or aromatic. Highly preferredoxygen bleaches also include 6-nonylamino-6-oxoperoxycaproic acid(NAPAA) as described in U.S. Pat. No. 4,634,551.

[0319] An extensive and exhaustive listing of useful oxygen bleaches,including inorganic peroxohydrates, organic peroxohydrates and theorganic peroxyacids, including hydrophilic and hydrophobic mono- ordi-peroxyacids, peroxycarboxylic acids, peroxyimidic acids,amidoperoxycarboxylic acids, or their salts including the calcium,magnesium, or mixed-cation salts, can be found in U.S. Pat. Nos.5,622,646 and 5,686,014.

[0320] Other useful peracids and bleach activators herein are in thefamily of imidoperacids and imido bleach activators. These includephthaloylimidoperoxycaproic acid and related arylimido-substituted andacyloxynitrogen derivatives. For listings of such compounds,preparations and their incorporation into laundry compositions includingboth granules and liquids, See U.S. Pat. No. 5,487,818; U.S. Pat. No.5,470,988, U.S. Pat. No. 5,466,825; U.S. Pat. No. 5,419,846; U.S. Pat.No. 5,415,796; U.S. Pat. No. 5,391,324; U.S. Pat. No. 5,328,634; U.S.Pat. No. 5,310,934; U.S. Pat. No. 5,279,757; U.S. Pat. No. 5,246,620;U.S. Pat. No. 5,245,075; U.S. Pat. No. 5,294,362; U.S. Pat. No.5,423,998; U.S. Pat. No. 5,208,340; U.S. Pat. No. 5,132,431 and U.S.Pat. No. 5,087385.

[0321] Useful diperoxyacids include, for example,1,12-diperoxydodecanedioic acid (DPDA); 1,9-diperoxyazelaic acid;diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalicacid; 2-decyldiperoxybutane-1,4-dioic acid; and4,4′-sulphonylbisperoxybenzoic acid.

[0322] More generally, the terms “hydrophilic” and “hydrophobic” usedherein in connection with any of the oxygen bleaches, especially theperacids, and in connection with bleach activators, are in the firstinstance based on whether a given oxygen bleach effectively performsbleaching of fugitive dyes in solution thereby preventing fabric grayingand discoloration and/or removes more hydrophilic stains such as tea,wine and grape juice—in this case it is termed “hydrophilic”. When theoxygen bleach or bleach activator has a significant stain removal,whiteness-improving or cleaning effect on dingy, greasy, carotenoid, orother hydrophobic soils, it is termed “hydrophobic”. The terms areapplicable also when referring to peracids or bleach activators used incombination with a hydrogen peroxide source. The current commercialbenchmarks for hydrophilic performance of oxygen bleach systems are:TAED or peracetic acid, for benchmarking hydrophilic bleaching. NOBS orNAPAA are the corresponding benchmarks for hydrophobic bleaching. Theterms “hydrophilic”, “hydrophobic” and “hydrotropic” with reference tooxygen bleaches including peracids and here extended to bleach activatorhave also been used somewhat more narrowly in the literature. Seeespecially Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 4.,pages 284-285. This reference provides a chromatographic retention timeand critical micelle concentration-based set of criteria, and is usefulto identify and/or characterize preferred sub-classes of hydrophobic,hydrophilic and hydrotropic oxygen bleaches and bleach activators thatcan be used in the present invention.

[0323] While not preferred for compositions of the present inventionwhich comprise detersive enzymes, the present invention compositions mayalso comprise as the bleaching agent a chlorine-type bleaching material.Such agents are well known in the art, and include for example sodiumdichloroisocyanurate (“NaDCC”), or sodium hypochlorite (NaOCl).

[0324] Bleach Activators

[0325] Bleach activators useful herein include amides, imides, estersand anhydrides. Commonly at least one substituted or unsubstituted acylmoiety is present, covalently connected to a leaving group as in thestructure R—C(O)-L. In one preferred mode of use, bleach activators arecombined with a source of hydrogen peroxide, such as the perborates orpercarbonates, in a single product. Conveniently, the single productleads to in situ production in aqueous solution (i.e., during thewashing process) of the percarboxylic acid corresponding to the bleachactivator. The product itself can be hydrous, for example a powder,provided that water is controlled in amount and mobility such thatstorage stability is acceptable. Alternately, the product can be ananhydrous solid or liquid. In another mode, the bleach activator oroxygen bleach is incorporated in a pretreatment product, such as a stainstick; soiled, pretreated substrates can then be exposed to furthertreatments, for example of a hydrogen peroxide source. With respect tothe above bleach activator structure RC(O)L, the atom in the leavinggroup connecting to the peracid-forming acyl moiety R(C)O— is mosttypically O or N. Bleach activators can have non-charged, positively ornegatively charged peracid-forming moieties and/or noncharged,positively or negatively charged leaving groups. One or moreperacid-forming moieties or leaving-groups can be present. See, forexample, U.S. Pat. No. 5,595,967, U.S. Pat. No. 5,561,235, U.S. Pat. No.5,560,862 or the bis-(peroxy-carbonic) system of U.S. Pat. No.5,534,179. Mixtures of suitable bleach activators can also be used.Bleach activators can be substituted with electron-donating orelectron-releasing moieties either in the leaving-group or in theperacid-forming moiety or moieties, changing their reactivity and makingthem more or less suited to particular pH or wash conditions. Forexample, electron-withdrawing groups such as NO₂ improve the efficacy ofbleach activators intended for use in mild-pH (e.g., from about 7.5- toabout 9.5) wash conditions.

[0326] An extensive and exhaustive disclosure of suitable bleachactivators and suitable leaving groups, as well as how to determinesuitable activators, can be found in U.S. Pat. Nos. 5,686,014 and5,622,646.

[0327] Cationic bleach activators include quaternary carbamate-,quaternary carbonate-, quaternary ester- and quaternary amide-types,delivering a range of cationic peroxyimidic, peroxycarbonic orperoxycarboxylic acids to the wash. An analogous but non-cationicpalette of bleach activators is available when quaternary derivativesare not desired. In more detail, cationic activators include quaternaryammonium-substituted activators of WO 96-06915, U.S. Pat. No. 4,751,015and 4,397,757, EP-A-284292, EP-A-331,229 and EP-A-03520. Also useful arecationic nitriles as disclosed in EP-A-303,520 and in European PatentSpecification 458,396 and 464,880. Other nitrile types haveelectron-withdrawing substituents as described in U.S. Pat. No.5,591,378.

[0328] Other bleach activator disclosures include GB 836,988; 864,798;907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522;EP-A-0174132; EP-A-0120591; U.S. Pat. Nos. 1,246,339; 3,332,882;4,128,494; 4,412,934 and 4,675,393, and the phenol sulfonate ester ofalkanoyl aminoacids disclosed in U.S. Pat. No. 5,523,434. Suitablebleach activators include any acetylated diamine types, whetherhydrophilic or hydrophobic in character.

[0329] Of the above classes of bleach precursors, preferred classesinclude the esters, including acyl phenol sulfonates, acyl alkyl phenolsulfonates or acyl oxybenzenesulfonates (OBS leaving-group); theacyl-amides; and the quaternary ammonium substituted peroxyacidprecursors including the cationic nitriles.

[0330] Preferred bleach activators include N,N,N′N′-tetraacetyl ethylenediamine (TAED) or any of its close relatives including the triacetyl orother unsymmetrical derivatives. TAED and the acetylated carbohydratessuch as glucose pentaacetate and tetraacetyl xylose are preferredhydrophilic bleach activators. Depending on the application, acetyltriethyl citrate, a liquid, also has some utility, as does phenylbenzoate.

[0331] Preferred hydrophobic bleach activators include sodiumnonanoyloxybenzene sulfonate (NOBS or SNOBS),N-(alkanoyl)aminoalkanoyloxy benzene sulfonates, such as4-[N-(nonanoyl)aminohexanoyloxy]-benzene sulfonate or (NACA-OBS) asdescribed in U.S. Pat. No. 5,534,642 and in EPA 0 355 384 A1,substituted amide types described in detail hereinafter, such asactivators related to NAPAA, and activators related to certainimidoperacid bleaches, for example as described in U.S. Pat. No.5,061,807, issued Oct. 29, 1991 and assigned to HoechstAktiengesellschaft of Frankfurt, Germany and Japanese Laid-Open PatentApplication (Kokai) No. 4-28799.

[0332] Another group of peracids and bleach activators herein are thosederivable from acyclic imidoperoxycarboxylic acids and salts thereof,See U.S. Pat. No. 5,415,796, and cyclic imidoperoxycarboxylic acids andsalts thereof, see U.S. Pat. Nos. 5,061,807, 5,132,431, 5,6542,69,5,246,620, 5,419,864 and 5,438,147.

[0333] Other suitable bleach activators include sodium-4-benzoyloxybenzene sulfonate (SBOBS); sodium-1-methyl-2-benzoyloxybenzene-4-sulphonate; sodium-4-methyl-3-benzoyloxy benzoate (SPCC);trimethyl ammonium toluyloxy-benzene sulfonate; or sodium3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS).

[0334] Bleach activators may be used in an amount of up to 20%,preferably from 0.1-10% by weight, of the composition, though higherlevels, 40% or more, are acceptable, for example in highly concentratedbleach additive product forms or forms intended for appliance automateddosing.

[0335] Highly preferred bleach activators useful herein areamide-substituted and an extensive and exhaustive disclosure of theseactivators can be found in U.S. Pat. Nos. 5,686,014 and 5,622,646.

[0336] Other useful activators, disclosed in U.S. Pat. No. 4,966,723,are benzoxazin-type, such as a C₆H4 ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)═N—. A highly preferred activator ofthe benzoxazin-type is:

[0337] Depending on the activator and precise application, goodbleaching results can be obtained from bleaching systems having within-use pH of from about 6 to about 13, preferably from about 9.0 toabout 10.5. Typically, for example, activators with electron-withdrawingmoieties are used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

[0338] Acyl lactam activators are very useful herein, especially theacyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams(see U.S. Pat. No. 5,503,639). See also U.S. Pat. No. 4,545,784 whichdiscloses acyl caprolactams, including benzoyl caprolactam adsorbed intosodium perborate. In certain preferred embodiments of the invention,NOBS, lactam activators, imide activators or amide-functionalactivators, especially the more hydrophobic derivatives, are desirablycombined with hydrophilic activators such as TAED, typically at weightratios of hydrophobic activator: TAED in the range of 1:5 to 5:1,preferably about 1:1. Other suitable lactam activators arealpha-modified, see WO 96-22350 Al, Jul. 25, 1996. Lactam activators,especially the more hydrophobic types, are desirably used in combinationwith TAED, typically at weight ratios of amido-derived or caprolactamactivators: TAED in the range of 1:5 to 5:1, preferably about 1:1. Seealso the bleach activators having cyclic amidine leaving-group disclosedin U.S. Pat. No. 5,552,556.

[0339] Nonlimiting examples of additional activators useful herein areto be found in U.S. Pat. No. 4,915,854, U.S. Pat. No. 4,412,934 and4,634,551. The hydrophobic activator nonanoyloxybenzene sulfonate (NOBS)and the hydrophilic tetraacetyl ethylene diamine (TAED) activator aretypical, and mixtures thereof can also be used.

[0340] Additional activators useful herein include those of U.S. Pat.No. 5,545,349.

[0341] Transition Metal Bleach Catalysts:

[0342] If desired, the bleaching compounds can be catalyzed by means ofa manganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. No. 5,246,621, U.S. Pat. No. 5,244,594; U.S. Pat. No. 5,194,416;U.S. Pat. No. 5,114,606; European Pat. App. Pub. Nos. 549,271A1,549,272A1, 544,440A2, 544,490A1; and PCT applications PCT/IB98/00298(Attorney Docket No. 6527×), PCT/1B98/00299 (Attorney Docket No. 6537),PCT/IB98/00300 (Attorney Docket No. 6525XL&), and PCT/IB98/00302(Attorney Docket No. 6524L#); Preferred examples of these catalystsinclude MnIV₂(u-0)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂,Mn^(III) ₂(u-O) 1(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,MnIV₄(u-0)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)-Mn^(IV) ₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. Nos. 4,430,243, 5,114,611, 5,622,646 and5,686,014. The use of manganese with various complex ligands to enhancebleaching is also reported in the following U.S. Pat. Nos. 4,728,455;5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and5,227,084.

[0343] Cobalt bleach catalysts useful herein are known, and aredescribed, for example, in M. L. Tobe, “Base Hydrolysis ofTransition-Metal Complexes”, Adv. Inorg. Bioinorg. Mech., (1983), 2,pages 1-94. The most preferred cobalt catalyst useful herein are cobaltpentaamine acetate salts having the formula [Co(NH₃)₅OAc] Ty, wherein“OAc” represents an acetate moiety and “Ty” is an anion, and especiallycobalt pentaamine acetate chloride, [Co(NH₃)₅OAc]Cl₂; as well as[Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc](SO₄);[Co(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)₂ (herein “PAC”). Thesecobalt catalysts are readily prepared by known procedures, such astaught for example in the Tobe article and the references cited therein,and in U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar. 7, 1989.

[0344] Compositions herein may also suitably include as a bleachcatalyst the class of transition metal complexes of a macropolycyclicrigid ligand. The phrase “macropolycyclic rigid ligand” is sometimesabbreviated as “MRL”. One useful MRL is [MnByclamC12], where “Bcyclam”is (5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane). See PCTapplications PCT/IB98/00298 (Attorney Docket No. 6527×), PCT/IB98/00299(Attorney Docket No. 6537), PCT/IB98/00300 (Attorney Docket No.6525XL&), and PCT/IB98/00302 (Attorney Docket No. 6524L#). The amountused is a catalytically effective amount, suitably about 1 ppb or more,for example up to about 99.9%, more typically about 0.001 ppm or more,preferably from about 0.05 ppm to about 500 ppm (wherein “ppb” denotesparts per billion by weight and “ppm” denotes parts per million byweight).

[0345] As a practical matter, and not by way of limitation, thecompositions and cleaning processes herein can be adjusted to provide onthe order of at least one part per hundred million of the active bleachcatalyst species in the aqueous washing medium, and will preferablyprovide from about 0.01 ppm to about 25 ppm, more preferably from about0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm toabout 5 ppm, of the bleach catalyst species in the wash liquor. In orderto obtain such levels in the wash liquor of an automatic washingprocess, typical compositions herein will comprise from about 0.0005% toabout 0.2%, more preferably from about 0.004% to about 0.08%, of bleachcatalyst, especially manganese or cobalt catalysts, by weight of thecleaning compositions.

[0346] Enzymatic Sources of Hydrogen Peroxide

[0347] On a different track from the bleach activators illustratedhereinabove, another suitable hydrogen peroxide generating system is acombination of a C₁-C₄ alkanol oxidase and a C₁-C₄ alkanol, especially acombination of methanol oxidase (MOX) and ethanol. Such combinations aredisclosed in WO 94/03003. Other enzymatic materials related tobleaching, such as peroxidases, haloperoxidases, oxidases, superoxidedismutases, catalases and their enhancers or, more commonly, inhibitors,may be used as optional ingredients in the instant compositions.

[0348] Oxygen Transfer Agents and Precursors

[0349] Also useful herein are any of the known organic bleach catalysts,oxygen transfer agents or precursors therefor. These include thecompounds themselves and/or their precursors, for example any suitableketone for production of dioxiranes and/or any of the hetero-atomcontaining analogs of dioxirane precursors or dioxiranes, such assulfonimines R¹R²C═NSO₂R³, see EP 446 982 A, published 1991 andsulfonyloxaziridines, see EP 446,981 A, published 1991. Preferredexamples of such materials include hydrophilic or hydrophobic ketones,used especially in conjunction with monoperoxysulfates to producedioxiranes in situ, and/or the imines described in U.S. Pat. No.5,576,282 and references described therein. Oxygen bleaches preferablyused in conjunction with such oxygen transfer agents or precursorsinclude percarboxylic acids and salts, percarbonic acids and salts,peroxymonosulfuric acid and salts, and mixtures thereof. See also U.S.Pat. No. 5,360,568; U.S. Pat. No. 5,360,569; U.S. Pat. No. 5,370,826 andU.S. Pat. No. 5,442,066.

[0350] Although oxygen bleach systems and/or their precursors may besusceptible to decomposition during storage in the presence of moisture,air (oxygen and/or carbon dioxide) and trace metals (especially rust orsimple salts or colloidal oxides of the transition metals) and whensubjected to light, stability can be improved by adding commonsequestrants (chelants) and/or polymeric dispersants and/or a smallamount of antioxidant to the bleach system or product. See, for example,U.S. Pat. No. 5,545,349. Antioxidants are often added to detergentingredients ranging from enzymes to surfactants. Their presence is notnecessarily inconsistent with use of an oxidant bleach; for example, theintroduction of a phase barrier may be used to stabilize an apparentlyincompatible combination of an enzyme and antioxidant, on one hand, andan oxygen bleach, on the other. Although commonly known substances canbe used as antioxidants, For example see U.S. Pat. Nos. 5,686,014,5,622,646, 5,055,218, 4,853,143, 4,539,130 and 4,483,778. Preferredantioxidants are 3,5-di-tert-butyl-4-hydroxytoluene,2,5-di-tert-butylhydroquinone and D,L-alpha-tocopherol.

[0351] Polymeric Soil Release Agent—The compositions according to thepresent invention may optionally comprise one or more soil releaseagents. Polymeric soil release agents are characterized by having bothhydrophilic segments, to hydrophilize the surface of hydrophobic fibers,such as polyester and nylon, and hydrophobic segments, to deposit uponhydrophobic fibers and remain adhered thereto through completion of thelaundry cycle and, thus, serve as an anchor for the hydrophilicsegments. This can enable stains occurring subsequent to treatment withthe soil release agent to be more easily cleaned in later washingprocedures.

[0352] If utilized, soil release agents will generally comprise fromabout 0.01% to about 10% preferably from about 0.1% to about 5%, morepreferably from about 0.2% to about 3% by weight, of the composition.

[0353] The following, all included herein by reference, describe soilrelease polymers suitable for us in the present invention. U.S. Pat. No.5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al. issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,702,857 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No.4,711,730 Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580Gosselink issued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al.,issued Dec. 28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25,1976; U.S. Pat. No. 3,893,929 Basadur, issued Jul. 8, 1975; and EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud et al.

[0354] Further suitable soil release agents are described in U.S. Pat.No. 4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.;U.S. Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681 Ruppert etal.; U.S. Pat. No. 4,220,918; U.S. Pat. No. 4,787,989; EP 279,134 A,1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE2,335,044 to Unilever N. V., 1974; all incorporated herein by reference.

[0355] Clay Soil Removal/Anti-redeposition Agents—The compositions ofthe present invention can also optionally contain water-solubleethoxylated amines having clay soil removal and antiredepositionproperties. Granular detergent compositions which contain thesecompounds typically contain from about 0.01% to about 10.0% by weight ofthe water-soluble ethoxylated amines; liquid detergent compositionstypically contain about 0.01% to about 5%.

[0356] A preferred soil release and anti-redeposition agent isethoxylated tetraethylene pentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. See U.S. Pat. No. 4,891,160, VanderMeer, issuedJan. 2, 1990 and WO 95/32272, published Nov. 30, 1995. Another type ofpreferred antiredeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

[0357] Polymeric Dispersing Agents—Polymeric dispersing agents canadvantageously be utilized at levels from about 0.1% to about 7%, byweight, in the compositions herein, especially in the presence ofzeolite and/or layered silicate builders. Suitable polymeric dispersingagents include polymeric polycarboxylates and polyethylene glycols,although others known in the art can also be used. It is believed,though it is not intended to be limited by theory, that polymericdispersing agents enhance overall detergent builder performance, whenused in combination with other builders (including lower molecularweight polycarboxylates) by crystal growth inhibition, particulate soilrelease, peptization, and anti-redeposition.

[0358] Polymeric polycarboxylate materials can be prepared bypolymerizing or copolymerizing suitable unsaturated monomers, preferablyin their acid form. Unsaturated monomeric acids that can be polymerizedto form suitable polymeric polycarboxylates include acrylic acid, maleicacid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

[0359] Particularly suitable polymeric polycarboxylates can be derivedfrom acrylic acid. The average molecular weight of such polymers in theacid form preferably ranges from about 2,000 to 10,000, more preferablyfrom about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.Soluble polymers of this type are known materials. Use of polyacrylatesof this type in detergent compositions has been disclosed, for example,in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967.

[0360] Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. The averagemolecular weight of such copolymers in the acid form preferably rangesfrom about 2,000 to 100,000, more preferably from about 5,000 to 75,000,most preferably from about 7,000 to 65,000. The ratio of acrylate tomaleate segments in such copolymers will generally range from about 30:1to about 1:1, more preferably from about 10:1 to 2:1. Solubleacrylate/maleate copolymers of this type are known materials which aredescribed in European Patent Application No. 66915, published Dec. 15,1982, as well as in EP 193,360, published Sep. 3, 1986, which alsodescribes such polymers comprising hydroxypropylacrylate. Still otheruseful dispersing agents include the maleic/acrylic/vinyl alcoholterpolymers. Such materials are also disclosed in EP 193,360, including,for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

[0361] Another polymeric material which can be included is polyethyleneglycol (PEG). PEG can exhibit dispersing agent performance as well asact as a clay soil removal-antiredeposition agent. Typical molecularweight ranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

[0362] Polyaspartate and polyglutamate dispersing agents may also beused, especially in conjunction with zeolite builders. Dispersing agentssuch as polyaspartate preferably have a molecular weight (avg.) of about10,000.

[0363] Other polymer types which may be more desirable forbiodegradability, improved bleach stability, or cleaning purposesinclude various terpolymers and hydrophobically modified copolymers,including those marketed by Rohm & Haas, BASF Corp., Nippon Shokubai andothers for all manner of water-treatment, textile treatment, ordetergent applications.

[0364] Brightener—Any optical brighteners or other brightening orwhitening agents known in the art can be incorporated at levelstypically from about 0.01% to about 1.2%, by weight, into the detergentcompositions herein when they are designed for fabric washing ortreatment.

[0365] Specific examples of optical brighteners which are useful in thepresent compositions are those identified in U.S. Pat. No. 4,790,856,issued to Wixon on Dec. 13, 1988. These brighteners include thePHORWHITE series of brighteners from Verona. Other brighteners disclosedin this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM;available from Ciba-Geigy; Arctic White CC and Arctic White CWD, the2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles;4,4′-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4′-bis(styryl)bisphenyls; andthe aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene;1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-styryl-naptho[1,2-d]oxazole; and2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton.

[0366] Polymeric Dye Transfer Inhibiting Agents—The compositions of thepresent invention may also include one or more materials effective forinhibiting the transfer of dyes from one fabric to another during thecleaning process. Generally, such dye transfer inhibiting agents includepolyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymersof N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

[0367] The amine N-oxide polymers typically have a ratio of amine to theamine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxidegroups present in the polyamine oxide polymer can be varied byappropriate copolymerization or by an appropriate degree of N-oxidation.The polyamine oxides can be obtained in almost any degree ofpolymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as “PVNO”. See U.S. Pat. No. 5,633,255 to Fredj.

[0368] The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

[0369] Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers(referred to as a class as “PVPVI”) are also preferred for use herein.Preferably the PVPVI has an average molecular weight range from 5,000 to1,000,000, more preferably from 5,000 to 200,000, and most preferablyfrom 10,000 to 20,000. (The average molecular weight range is determinedby light scattering as described in Barth, et al., Chemical Analysis,Vol. 113. “Modem Methods of Polymer Characterization”, the disclosuresof which are incorporated herein by reference.) The PVPVI copolymerstypically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidonefrom 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferablyfrom 0.6:1 to 0.4:1. These copolymers can be either linear or branched.

[0370] The present invention compositions also may employ apolyvinylpyrrolidone (“PVP”) having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol (“PEG”)having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

[0371] The detergent compositions herein may also optionally containfrom about 0.005% to 5% by weight of certain types of hydrophilicoptical brighteners which also provide a dye transfer inhibition action.If used, the compositions herein will preferably comprise from about0.01% to 1% by weight of such optical brighteners.

[0372] The hydrophilic optical brighteners useful in the presentinvention include, for example4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt (Tinopal-UNPA-GX),4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid di-sodium salt (Tinopal 5BM-GX) and4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt (Tinopal AMS-GX) all by Ciba Geigy Corporation.

[0373] The specific optical brightener species selected for use in thepresent invention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory the extent to which brighteners deposit on fabrics inthe wash solution can be defined by a parameter called the “exhaustioncoefficient”. The exhaustion coefficient is in general defined as theratio of a) the brightener material deposited on fabric to b) theinitial brightener concentration in the wash liquor. Brighteners withrelatively high exhaustion coefficients are the most suitable forinhibiting dye transfer in the context of the present invention.

[0374] Other, conventional optical brightener types can optionally beused in the present compositions to provide conventional fabric“brightness” benefits, rather than a dye transfer inhibiting effect.Such usage is conventional and well-known to detergent formulations.

[0375] Chelating Agents—The detergent compositions herein may alsooptionally contain one or chelating agents, particularly chelatingagents for adventitious transition metals. Those commonly found in washwater include iron and/or manganese in water-soluble, colloidal orparticulate form, and may be associated as oxides or hydroxides, orfound in association with soils such as humic substances. Preferredchelants are those which effectively control such transition metals,especially including controlling deposition of such transition-metals ortheir compounds on fabrics and/or controlling undesired redox reactionsin the wash medium and/or at fabric or hard surface interfaces. Suchchelating agents include those having low molecular weights as well aspolymeric types, typically having at least one, preferably two or moredonor heteroatoms such as O or N, capable of co-ordination to atransition-metal, Common chelating agents can be selected from the groupconsisting of aminocarboxylates, aminophosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof, all as hereinafter defined.

[0376] Aminocarboxylates useful as optional chelating agents includeethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetrapropionates,triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, andethanoldiglycines, their alkali metal, ammonium, and substitutedammonium salts, and mixtures thereof.

[0377] Aminophosphonates are also suitable for use as chelating agentsin the compositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) such as DEQUEST.Preferably, these amino phosphonates do not contain alkyl or alkenylgroups having more than about 6 carbon atoms.

[0378] Polyfunctionally-substituted aromatic chelating agents are alsouseful in the compositions herein. See U.S. Pat. No. 3,812,044, issuedMay 21, 1974, to Connor et al. Preferred compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

[0379] A preferred biodegradable chelator for use herein isethylenediamine disuccinate (“EDDS”), especially the [S,S] isomer asdescribed in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman andPerkins.

[0380] The compositions herein may also contain water-soluble methylglycine diacetic acid (MGDA) salts (or acid form) as a chelant orco-builder useful with, for example, insoluble builders such aszeolites, layered silicates and the like.

[0381] If utilized, chelating agents will generally comprise from about0.001% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, chelating agents will comprise from about 0.01%to about 3.0% by weight of such compositions.

[0382] Suds Suppressors—Compounds for reducing or suppressing theformation of suds can be incorporated into the compositions of thepresent invention when required by the intended use, especially washingof laundry in washing appliances. Other compositions, such as thosedesigned for hand-washing, may desirably be high-sudsing and may omitsuch ingredients Suds suppression can be of particular importance in theso-called “high concentration cleaning process” as described in U.S.Pat. No. 4,489,455 and 4,489,574 and in front-loading European-stylewashing machines.

[0383] A wide variety of materials may be used as suds suppressors andare well known in the art. See, for example, Kirk Othmer Encyclopedia ofChemical Technology, Third Edition, Volume 7, pages 430-447 (Wiley,1979).

[0384] The compositions herein will generally comprise from 0% to about10% of suds suppressor. When utilized as suds suppressors,monocarboxylic fatty acids, and salts thereof, will be present typicallyin amounts up to about 5%, preferably 0.5%-3% by weight, of thedetergent composition. although higher amounts may be used. Preferablyfrom about 0.01% to about 1% of silicone suds suppressor is used, morepreferably from about 0.25% to about 0.5%. These weight percentagevalues include any silica that may be utilized in combination withpolyorganosiloxane, as well as any suds suppressor adjunct materialsthat may be utilized. Monostearyl phosphate suds suppressors aregenerally utilized in amounts ranging from about 0.1% to about 2%, byweight, of the composition. Hydrocarbon suds suppressors are typicallyutilized in amounts ranging from about 0.01% to about 5.0%, althoughhigher levels can be used. The alcohol suds suppressors are typicallyused at 0.2%-3% by weight of the finished compositions.

[0385] Alkoxylated Polycarboxylates—Alkoxylated polycarboxylates such asthose prepared from polyacrylates are useful herein to provideadditional grease removal performance. Such materials are described inWO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein byreference. Chemically, these materials comprise polyacrylates having oneethoxy side-chain per every 7-8 acrylate units. The side-chains are ofthe formula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12.The side-chains are ester-linked to the polyacrylate “backbone” toprovide a “comb” polymer type structure. The molecular weight can vary,but is typically in the range of about 2000 to about 50,000. Suchalkoxylated polycarboxylates can comprise from about 0.05% to about 10%,by weight, of the compositions herein.

[0386] Fabric Softeners—Various through-the-wash fabric softeners,especially the impalpable smectite clays of U.S. Pat. No. 4,062,647,Storm and Nirschl, issued Dec. 13, 1977, as well as other softener claysknown in the art, can optionally be used typically at levels of fromabout 0.5% to about 10% by weight in the present compositions to providefabric softener benefits concurrently with fabric cleaning. Claysofteners can be used in combination with amine and cationic softenersas disclosed, for example, in U.S. Pat. No. 4,375,416, Crisp et al, Mar.1, 1983 and U.S. Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981.Moreover, in laundry cleaning methods herein, known fabric softeners,including biodegradable types, can be used in pretreat, mainwash,post-wash and dryer-added modes.

[0387] Perfumes—Perfumes and perfumery ingredients useful in the presentcompositions and processes comprise a wide variety of natural andsynthetic chemical ingredients, including, but not limited to,aldehydes, ketones, esters, and the like. Also included are variousnatural extracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes typically comprise from about 0.01%to about 2%, by weight, of the detergent compositions herein, andindividual perfumery ingredients can comprise from about 0.0001% toabout 90% of a finished perfume composition.

[0388] Non-limiting examples of perfume ingredients useful hereininclude: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone;methyl dihydrojasmonate; methyl1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone;7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

[0389] Particularly preferred perfume materials are those that providethe largest odor improvements in finished product compositionscontaining cellulases. These perfumes include but are not limited to:hexyl cinnamic aldehyde;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

[0390] Other perfume materials include essential oils, resinoids, andresins from a variety of sources including, but not limited to: Perubalsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil,benzoin resin, coriander and lavandin. Still other perfume chemicalsinclude phenyl ethyl alcohol, terpineol, linalool, linalyl acetate,geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzylacetate, and eugenol. Carriers such as diethylphthalate can be used inthe finished perfume compositions.

[0391] Other Detergent Ingredients—A wide variety of other ingredientsuseful in detergent compositions can be included in the compositionsherein, including other active ingredients, carriers, hydrotropes,processing aids, dyes or pigments, solvents for liquid formulations,solid fillers for bar compositions, etc. If high sudsing is desired,suds boosters such as the C₁₀-C₁₆ alkanolamides can be incorporated intothe compositions, typically at 1%-10% levels. The C₁₀-C₁₄ monoethanoland diethanol amides illustrate a typical class of such suds boosters.Use of such suds boosters with high sudsing adjunct surfactants such asthe amine oxides, betaines and sultaines noted above is alsoadvantageous. If desired, water-soluble magnesium and/or calcium saltssuch as MgCl₂, MgSO₄, CaCl₂, CaSO₄ and the like, can be added at levelsof, typically, 0.1%-2%, to provide additional suds and to enhance greaseremoval performance, especially for liquid dishwashing purposes.

[0392] Various detersive ingredients employed in the presentcompositions optionally can be further stabilized by absorbing saidingredients onto a porous hydrophobic substrate, then coating saidsubstrate with a hydrophobic coating. Preferably, the detersiveingredient is admixed with a surfactant before being absorbed into theporous substrate. In use, the detersive ingredient is released from thesubstrate into the aqueous washing liquor, where it performs itsintended detersive function.

[0393] Liquid detergent compositions can contain water and othersolvents as carriers. Low molecular weight primary or secondary alcoholsexemplified by methanol, ethanol, propanol, and isopropanol aresuitable. Monohydric alcohols are preferred for solubilizing surfactant,but polyols such as those containing from 2 to about 6 carbon atoms andfrom 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethyleneglycol, glycerine, and 1,2-propanediol) can also be used. Thecompositions may contain from 5% to 90%, typically 10% to 50% of suchcarriers.

[0394] The detergent compositions herein will preferably be formulatedsuch that, during use in aqueous cleaning operations, the wash waterwill have a pH of between about 6.5 and about 11, preferably betweenabout 7.0 and 10.5, more preferably between about 7.0 to about 9.5.Liquid dishwashing product formulations preferably have a pH betweenabout 6.8 and about 9.0. Laundry products are typically at pH 9-11.Techniques for controlling pH at recommended usage levels include theuse of buffers, alkalis, acids, etc., and are well known to thoseskilled in the art.

[0395] Conventional Skin Care Additives

[0396] The skin care compositions of the present invention may contain avariety of other ingredients such as are conventionally used in a givenproduct type provided they do not unacceptably alter the benefits of theinvention. These optional components should be suitable for applicationto human skin, that is, when incorporated into the composition they aresuitable for use in contact with human skin without undue toxicity,incompatibility, instability, allergic response, and the like within thescope of sound medical or formulator's judgment. The CTFA CosmeticIngredient Handbook, Second Edition (1992) describes a wide variety ofnonlimiting cosmetic and pharmaceutical ingredients commonly used in theskin care industry, which are suitable for use in the compositions ofthe present invention. Examples of these ingredient classes include:abrasives, absorbents, aesthetic components such as perfumes, pigments,colorings/colorants, essential oils, skin sensates, astringents, etc.(e.g., clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyllactate, witch hazel distillate), anti-acne agents (e.g., resorcinol,sulfur, salicylic acid, erythromycin, zinc, etc.), anti-caking agents,antifoaming agents, antimicrobial agents (e.g., iodopropylbutylcarbamate), antioxidants, binders, biological additives, bufferingagents, bulking agents, chelating agents, chemical additives, colorants,cosmetic astringents, cosmetic biocides, denaturants, drug astringents,external analgesics, film formers or materials, e.g., polymers, foraiding the film-forming properties and substantivity of the composition(e.g., copolymer of eicosene and vinyl pyrrolidone), humectants,opacifying agents, pH adjusters, propellants, reducing agents,sequestrants, skin bleaching agents (or lightening agents) (e.g.,hydroquinone, kojic acid, ascorbic acid, magnesium ascorbyl phosphate,ascorbyl glucosamine), skin-conditioning agents (humectants, includingmiscellaneous and occlusive), skin soothing and/or healing agents (e.g.,panthenol and derivatives (e.g., ethyl panthenol), aloe vera,pantothenic acid and its derivatives, allantoin, bisabolol, anddipotassium glycyrrhizinate), skin treating agents including agents forpreventing, retarding, arresting, and/or reversing skin wrinkles (e.g.,alpha-hydroxy acids such as lactic acid and glycolic acid andbeta-hydroxy acids such as salicylic acid), thickeners, and vitamins andderivatives thereof (e.g. tocopherol, tocopherol acetate, retinoic acid,retinol, retinoids, retinyl palmitate, niacin, niacinamide, and thelike).

[0397] The skin care compositions of the present invention may containone or more of such optional components. Preferred skin carecompositions optionally contain one or more materials selected from UVBsunscreen actives, anti-acne actives, artificial tanning agents,humectants, moisturizers, skin conditioners, and thickening/structuringagents.

[0398] UVB Sunscreen Active

[0399] The skin care compositions of the present invention can comprisea UVB sunscreen active which absorbs UV radiation having a wavelength offrom about 290 nm to about 320 nm. As used herein, the UVB sunscreenactive means an active other than the dibenzoylmethane sunscreen activewhich itself may possess UVB absorption properties. The skin carecompositions should comprise an amount of the UVB active effective toprovide UVB protection either independently or in combination with otherUV protective actives which may be present in the skin care composition,preferably from about 0.1% to about 10%, more preferably from about 0.1%to about 4%, and most preferably from about 0.5% to about 2.5% by weightof the composition.

[0400] A wide variety of UVB sunscreen actives, including both organicsunscreen actives and inorganic physical sunblocks, are suitable for useherein. Nonlimiting examples of such sunscreen actives are described inU.S. Pat. No. 5,087,445 issued Feb. 11, 1992 to Haffey et al.; and U.S.Pat. Nos. 5,073,371 and 5,073,372, both issued on Dec. 17, 1991 toTurner et al. Nonlimiting examples of suitable physical sunblocks aredescribed in CTFA International Cosmetic Ingredient Dictionary, Sixthedition, 1995, pp. 1026-28, and 1103.

[0401] Preferred UVB sunscreen actives are selected from groupconsisting of 2-phenyl-benzimidazole-5-sulfonic acid, octocrylene, TEAsalicylate, octyl dimethyl PABA, zinc oxide, titanium dioxide, andmixtures thereof. A preferred organic sunscreen active is2-phenyl-benzimidazole-5-sulfonic acid while preferred inorganicphysical sunblocks are zinc oxide, titanium dioxide, and mixturesthereof. Salt and acid-neutralized forms of the acidic sunscreens arealso contemplated herein.

[0402] When used, the physical sunblocks are present in an amount suchthat the present skin care compositions are transparent on the skin(i.e., non-whitening), preferably less than or equal to about 5%. Whentitanium dioxide is used, it can have an anatase, rutile, or amorphousstructure. Physical sunblock particles, e.g., titanium dioxide and zincoxide, can be uncoated or coated with a variety of materials including,but not limited to, amino acids; aluminum compounds such as alumina,aluminum stearate, aluminum laurate, and the like; carboxylic acids andtheir salts, e.g., stearic acid and its salts; phospholipids such aslecithin; organic silicone compounds; inorganic silicone compounds suchas silica and silicates; and mixtures thereof. A preferred titaniumdioxide is commercially available from Tayca (Japan) and is distributedby Tri-K Industries (Emerson, N.J.) under the MT micronized series(e.g., MT 100SAS).

[0403] Anti-Acne Actives

[0404] The skin care compositions of the present invention may compriseone or more anti-acne actives. Examples of useful anti-acne actives aredescribed in further detail in U.S. Pat. No. 5,607,980, issued to McAteeet al., on Mar. 4, 1997.

[0405] Artificial Tanning Agents

[0406] The skin care compositions of the present invention can compriseone or more artificial tanning agents. Suitable tanning agents includedihydroxyacetone, tyrosine, tyrosine esters and phopho-pho-DOPA. See TheMerck Index, Tenth Edition, entry 3167, p. 463 (1983), and“Dihydroxyacetone for Cosmetics”, E. Merck Technical Bulletin, 03-304110, 319 897, 180 588.

[0407] Structuring Agent

[0408] The skin care compositions of the present invention may contain astructuring agent. Structuring agents are particularly preferred in theoil-in-water emulsions of the present invention. Without being limitedby theory, it is believed that the structuring agent assists inproviding rheological characteristics to the skin care composition whichcontribute to the stability of the composition. For example, thestructuring agent tends to assist in the formation of the liquidcrystalline gel network structures. The structuring agent may alsofunction as an emulsifier or surfactant. Preferred skin carecompositions of this invention comprise from about 0.5% to about 20%,more preferably from about 1% to about 10%, most preferably from about1% to about 5%, of one or more structuring agents.

[0409] The preferred structuring agents for use in the skin carecompositions of the present invention are selected from the groupconsisting of stearic acid, palmitic acid, stearyl alcohol, cetylalcohol, behenyl alcohol, stearic acid, palmitic acid, the polyethyleneglycol ether of stearyl alcohol having an average of about 1 to about 21ethylene oxide units, the polyethylene glycol ether of cetyl alcoholhaving an average of about 1 to about 5 ethylene oxide units, andmixtures thereof. More preferred structuring agents for use in the skincare compositions of the present invention are selected from the groupconsisting of stearyl alcohol, cetyl alcohol, behenyl alcohol, thepolyethylene glycol ether of stearyl alcohol having an average of about2 ethylene oxide units (steareth-2), the polyethylene glycol ether ofstearyl alcohol having an average of about 21 ethylene oxide units(steareth-21), the polyethylene glycol ether of cetyl alcohol having anaverage of about 2 ethylene oxide units, and mixtures thereof. Even morepreferred structuring agents are selected from the group consisting ofstearic acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenylalcohol, steareth-2, steareth-21, and mixtures thereof.

[0410] Thickening Agent (Including Thickeners and Gelling Agents)

[0411] The skin care compositions of the present invention can compriseone or more thickening agents, preferably from about 0.1% to about 5%,more preferably from about 0.1% to about 3%, and most preferably fromabout 0.25% to about 2%, by weight of the composition.

[0412] Nonlimiting classes of thickening agents include those selectedfrom the group consisting of:

[0413] Carboxylic Acid Polymers—These polymers are crosslinked compoundscontaining one or more monomers derived from acrylic acid, substitutedacrylic acids, and salts and esters of these acrylic acids and thesubstituted acrylic acids, wherein the crosslinking agent contains twoor more carbon-carbon double bonds and is derived from a polyhydricalcohol. Polymers useful in the present invention are more fullydescribed in U.S. Pat. No. 5,087,445, to Haffey et al., issued Feb. 11,1992; U.S. Pat. No. 4,509,949, to Huang et al., issued Apr. 5, 1985;U.S. Pat. No. 2,798,053, to Brown, issued Jul. 2, 1957; and in CTFAInternational Cosmetic Ingredient Dictionary, Fourth edition, 1991, pp.12 and 80.

[0414] Examples of commercially available carboxylic acid polymersuseful herein include the carbomers, which are homopolymers of acrylicacid crosslinked with allyl ethers of sucrose or pentaerytritol. Thecarbomers are available as the Carbopol® 900 series from B. F. Goodrich(e.g., Carbopol® 954). In addition, other suitable carboxylic acidpolymeric agents include copolymers of C₁₀₋₃₀ alkyl acrylates with oneor more monomers of acrylic acid, methacrylic acid, or one of theirshort chain (i.e. C₁₋₄ alcohol) esters, wherein the crosslinking agentis an allyl ether of sucrose or pentaerytritol. These copolymers areknown as acrylates/C₁₀₋₃₀ alkyl acrylate crosspolymers and arecommercially available as Carbopol® 1342, Carbopol® 1382, Pemulen TR-1,and Pemulen TR-2, from B. F. Goodrich. In other words, examples ofcarboxylic acid polymer thickeners useful herein are those selected fromthe group consisting of carbomers, acrylates/C₁₀-C₃₀ alkyl acrylatecrosspolymers, and mixtures thereof.

[0415] Crosslinked Polyacrylate Polymers—The skin care compositions ofthe present invention can optionally comprise crosslinked polyacrylatepolymers useful as thickeners or gelling agents including both cationicand nonionic polymers, with the cationics being generally preferred.Examples of useful crosslinked nonionic polyacrylate polymers andcrosslinked cationic polyacrylate polymers are those described in U.S.Pat. No. 5,100,660, to Hawe et al., issued Mar. 31, 1992; U.S. Pat. No.4,849,484, to Heard, issued Jul. 18, 1989; U.S. Pat. No. 4,835,206, toFarrar et al., issued May 30, 1989; U.S. Pat. No. 4,628,078 to Glover etal. issued Dec. 9, 1986; U.S. Pat. No. 4,599,379 to Flesher et al.issued Jul. 8, 1986; and EP 228,868, to Farrar et al., published Jul.15, 1987.

[0416] Polyacrylamide Polymers—The skin care compositions of the presentinvention can optionally comprise polyacrylamide polymers, especiallynonionic polyacrylamide polymers including substituted branched orunbranched polymers. Most preferred among these polyacrylamide polymersis the nonionic polymer given the CTFA designation polyacrylamide andisoparaffin and laureth-7, available under the Tradename Sepigel 305from Seppic Corporation (Fairfield, N.J.).

[0417] Other polyacrylamide polymers useful herein include multi-blockcopolymers of acrylamides and substituted acrylamides with acrylic acidsand substituted acrylic acids. Commercially available examples of thesemulti-block copolymers include Hypan SR150H, SS500V, SS500W, SSSA100H,from Lipo Chemicals, Inc., (Patterson, N.J.).

[0418] Polysaccharides—A wide variety of polysaccharides are usefulherein. “Polysaccharides” refer to gelling agents which contain abackbone of repeating sugar (i.e. carbohydrate) units. Nonlimitingexamples of polysaccharide gelling agents include those selected fromthe group consisting of cellulose, carboxymethyl hydroxyethylcellulose,cellulose acetate propionate carboxylate, hydroxyethylcellulose,hydroxyethyl ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methyl hydroxyethylcellulose, microcrystallinecellulose, sodium cellulose sulfate, and mixtures thereof. Also usefulherein are the alkyl substituted celluloses. In these polymers, thehydroxy groups of the cellulose polymer is hydroxyalkylated (preferablyhydroxyethylated or hydroxypropylated) to form a hydroxyalkylatedcellulose which is then further modified with a C₁₀-C₃₀ straight chainor branched chain alkyl group through an ether linkage. Typically thesepolymers are ethers of C₁₀-C₃₀ straight or branched chain alcohols withhydroxyalkylcelluloses. Examples of alkyl groups useful herein includethose selected from the group consisting of stearyl, isostearyl, lauryl,myristyl, cetyl, isocetyl, cocoyl (i.e. alkyl groups derived from thealcohols of coconut oil), palmityl, oleyl, linoleyl, linolenyl,ricinoleyl, behenyl, and mixtures thereof. Preferred among the alkylhydroxyalkyl cellulose ethers is the material given the CTFA designationcetyl hydroxyethylcellulose, which is the ether of cetyl alcohol andhydroxyethylcellulose. This material is sold under the tradenameNatrosol® CS Plus from Aqualon Corporation (Wilmington, Del.).

[0419] Other useful polysaccharides include scleroglucans comprising alinear chain of (1-3) linked glucose units with a (1-6) linked glucoseevery three units, a commercially available example of which isClearogel™ CS11 from Michel Mercier Products Inc. (Mountainside, N.J.).

[0420] Gums—Other thickening and gelling agents useful herein includematerials which are primarily derived from natural sources. Nonlimitingexamples of these gelling agent gums include materials selected from thegroup consisting of acacia, agar, algin, alginic acid, ammoniumalginate, amylopectin, calcium alginate, calcium carrageenan, carnitine,carrageenan, dextrin, gelatin, gellan gum, guar gum, guarhydroxypropyltrimonium chloride, hectorite, hyaluroinic acid, hydratedsilica, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, kelp,locust bean gum, natto gum, potassium alginate, potassium carrageenan,propylene glycol alginate, sclerotium gum, sodium carboxymethyl dextran,sodium carrageenan, tragacanth gum, xanthan gum, and mixtures thereof.

[0421] Preferred skin care compositions of the present invention includea thickening agent selected from the group consisting of carboxylic acidpolymers, crosslinked polyacrylate polymers, polyacrylamide polymers,and mixtures thereof, more preferably selected from the group consistingof carboxylic acid polymers, polyacrylamide polymers, and mixturesthereof.

[0422] Humectants, Moisturizers, and Skin Conditioners

[0423] Preferred skin care compositions optionally comprise one or morehumectants, moisturizers, or skin conditioners. A variety of thesematerials can be employed and each can be present at a level of fromabout 0.01% to about 20%, more preferably from about 0.1% to about 10%,and most preferably from about 0.5% to about 7%. These materialsinclude, but are not limited to, guanidine; glycolic acid and glycolatesalts (e.g. ammonium and quaternary alkyl ammonium); lactic acid andlactate salts (e.g. ammonium and quaternary alkyl ammonium); aloe verain any of its variety of forms (e.g., aloe vera gel); polyhydroxyalcohols such as sorbitol, glycerol, hexanetriol, propylene glycol,butylene glycol, hexylene glycol and the like; polyethylene glycols;sugars and starches; sugar and starch derivatives (e.g., alkoxylatedglucose); hyaluronic acid; lactamide monoethanolamine; acetamidemonoethanolamine; and mixtures thereof.

[0424] Also useful herein are the propoxylated glycerols described inU.S. Pat. No. 4,976,953, to Orr et al., issued Dec. 11, 1990.

[0425] Also useful are various C₁-C₃₀ monoesters and polyesters ofsugars and related materials. These esters are derived from a sugar orpolyol moiety and one or more carboxylic acid moieties. Such estermaterials are further described in, U.S. Pat. No. 2,831,854, U.S. Pat.No. 4,005,196, to Jandacek, issued Jan. 25, 1977; U.S. Pat. No.4,005,195, to Jandacek, issued Jan. 25, 1977, U.S. Pat. No. 5,306,516,to Letton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,306,515, toLetton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,305,514, to Lettonet al., issued Apr. 26, 1994; U.S. Pat. No. 4,797,300, to Jandacek etal., issued Jan. 10, 1989; U.S. Pat. No. 3,963,699, to Rizzi et al,issued Jun. 15, 1976; U.S. Pat. No. 4,518,772, to Volpenhein, issued May21, 1985; and U.S. Pat. No. 4,517,360, to Volpenhein, issued May 21,1985.

[0426] Emulsifiers

[0427] The skin care compositions of the present invention can alsocomprise one or more emulsifiers. Emulsifiers generally serve to reducethe in interfacial tension between phases and improve the formulationand stability of an emulsion. Suitable emulsifiers include a widevariety of nonionic, cationic, anionic, and zwitterionic emulsifiers.See McCutcheon's, Detergents and Emulsifiers, North American Edition(1986), published by Allured Publishing Corporation; U.S. Pat. No.5,011,681 issued to Ciotti et al. on Apr. 30, 1991; U.S. Pat. No.4,421,769 issued to Dixon et al. on Dec. 20, 1983; and U.S. Pat. No.3,755,560 issued to Dickert et al. on Aug. 28, 1973.

[0428] Suitable emulsifier types include esters of glycerin, esters ofpropylene glycol, fatty acid esters of polyethylene glycol, fatty acidesters of polypropylene glycol, esters of sorbitol, esters of sorbitananhydrides, carboxylic acid copolymers, esters and ethers of glucose,ethoxylated ethers, ethoxylated alcohols, alkyl phosphates,polyoxyethylene fatty ether phosphates, fatty acid amides, acyllactylates, soaps and mixtures thereof.

[0429] Suitable emulsifiers can include, but are not limited to, TEAstearate, DEA oleth-3 phosphate, polyethylene glycol 20 sorbitanmonolaurate (polysorbate 20), polyethylene glycol 5 soya sterol,steareth-2, steareth-20, steareth-21, ceteareth-20, PPG-2 methyl glucoseether distearate, ceteth-10, polysorbate 80, cetyl phosphate, potassiumcetyl phosphate, diethanolamine cetyl phosphate, polysorbate 60,glyceryl stearate, PEG-100 stearate, and mixtures thereof. Preferredemulsifiers are steareth-2, steareth-21, TEA stearate, diethanolaminecetyl phosphate, potassium cetyl phosphate, and mixtures thereof. Theemulsifier can be used individually or as a mixture of two or more andcomprises from about 0.1% to about 10%, more preferably from about 0.15%to about 7%, and most preferably from about 0.25% to about 5% of thecompositions of the present invention.

[0430] Conventional Personal Cleansing Additive

[0431] These are additives which are conventionally used in personalcleansing compositions, such as toilet soaps, body washes, shampoos andmedicated wipes. Examples of these are conditioning agents, conventionalpersonal care polymer, antidandruff agent, surfactant; and mixturesthereof. These conventional personal cleansing additives are just someof the possible ingredients which can be conventionally added topersonal cleansing compositions.

[0432] The conditioning agents, useful in the present invention can befurther selected from the group comprising non-volatile hydrocarbonsconditioning agents, silicone conditioning agents and mixtures thereof.

[0433] The conventional personal care polymers useful in the presentinvention can be further selected from the group comprising depositionpolymers, styling polymers and solvent, dispersed phase polymers, andmixtures thereof.

[0434] The personal cleansing compositions of the present invention isin the form of a liquid or a liquid gel. It can contain for example,suspended ingredients, more than one phase etc. Effectively the personalcleansing compositions of the present invention can be in the form ofany type of liquid or liquid gel and contain any additive conventionallyadded to personal cleansing compositions, such as shampoos, body washgels, bath gels etc.

[0435] For more information and additional examples of conventionalpersonal cleansing additives see copending U.S. Patent Application No.60/061,916, Attorney docket No 6884P, filed on Oct. 14, 1997 and U.S.Patent Application No. 60/061,975, Attorney docket No 6882P, filed onOct. 14, 1997, both assigned to Procter & Gamble.

[0436] Suitable conventional personal cleansing additives include antistatic agents, dyes, diluents, emollient oils (such as polyisobutylene,mineral oil, petrolatum and isocetyl stearyl stearate), pearlescentaids, foam boosters, styling polymer, pediculocides, dispersed phasepolymers, hydrotropes, hair or skin conditioning agents such asnonvolatile silicone conditioning agents and nonvolatile organicconditioning agents, solvent pH adjusting agents, perfumes,preservatives, low viscosity surfactant soluble conditioning oil,electrolytes, amphiphiles, proteins, phase separation initiator,cationic spreading agents, such as cationic surfactants, antioxidants;chelators and sequestrants, surfactants, antidandruff agent such asplatelet pyridinethione salt crystal, sulfur, octopirox, seleniumsulfide, ketoconazole and pyridinethione salts, organic depositionpolymers and aesthetic components such as fragrances, colorings,essential oils, skin sensates, astringents, suspending agent skinsoothing agents, aqueous liquid carrier, skin healing agents and thelike, nonlimiting examples of these aesthetic components includepanthenol and derivatives (e.g. ethyl panthenol), pantothenic acid andits derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol,menthyl lactate, witch hazel distillate, allantoin, (?)bisabolol,dipotassium glycyrrhizinate and the like, sunscreens, thickeners,vitamins and derivatives thereof (e.g., ascorbic acid, vitamin E,tocopheryl acetate, retinoic acid, retinol, retinoids, and the like),and viscosity adjusting agents. This list of conventional personalcleansing additives is not meant to be exclusive, and other conventionalpersonal cleansing additives can be used.

[0437] For more information and additional examples of conditioningagents see copending U.S. patent application Ser. No. 08/733,046,Attorney docket No 6303; filed on Oct. 16, 1996 and U.S. patentapplication Ser. No. 08/738,156, Attorney docket No 6331, filed on Oct.25, 1996. See also U.S. patent application No. 4,741,855. All three ofthese references are incorporated herein by reference.

[0438] Suitable suspending agents are described in U.S. Pat. Nos.4,741,855, 4,788,006, 2,798,053, and 4,704,272, which description isincorporated herein by reference.

[0439] For suitable deposition polymers see copending U.S. patentapplication Ser. No. 08/852,166, Attorney docket No 4519RC2, filed May6, 1997, Attorney docket No 6331 filed on Oct. 25, 1996; and Attorneydocket No 6766P filed on July 21st, 1997 (above), all of which areincorporated herein by reference.

[0440] See copending U.S. patent applications Ser. No. 08/738,211,Attorney docket No 6327 filed on Oct. 25, 1996 and No. 60/053,319,Attorney docket No 6766P filed on Jul. 21, 1997, both of which areincorporated herein by reference.

[0441] Examples of some suitable styling polymers are described in U.S.Pat. No. 5,120,531, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,120,532, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,104,642, to Wells et al., issued Apr. 14, 1992; U.S. Pat. No.4,272,511, to Papantoniou et al., issued Jun. 9, 1981; U.S. Pat. No.4,963,348, to Bolich et al., issued Oct. 16, 1990, EPO Application90307528.1, published as EPO Application 0 408 311 A2 on Jan. 11, 1991,Hayama, et al.; U.S. Pat. No. 5,061,481, issued Oct. 29, 1991, Suzuki etal.; U.S. Pat. No. 5,106,609, Bolich et al., issued Apr. 21, 1992; U.S.Pat. No. 5,100,658, Bolich et al., issued Mar. 31, 1992; U.S. Pat. No.5,100,657, Ansher-Jackson, et al., issued Mar. 31, 1992; U.S. Pat. No.5,104,646, Bolich et al., issued Apr. 14, 1992; U.S. Ser. No.07/758,319, Bolich et al, filed Aug. 27, 1991, U.S. Ser. No. 07/758,320,Torgerson et al., filed Aug. 27, 1991, and U.S. Pat. No. 4,196,190, toGehman et al., issued Apr. 1, 1980, which descriptions are incorporatedherein by reference.

[0442] For suitable dispersed phase polymer see also copending U.S.patent application Ser. No. 08/786,521, Attorney docket No 6484 filed onJan. 21, 1997, which is incorporated herein by reference.

[0443] For suitable phase separation initiators see copending U.S.Patent applications No. 60/061,916, Attorney docket No 6884P filed onOct. 14, 1997 and U.S. Patent applications No. 60/061,975, Attorneydocket No 6882P filed on Oct. 14, 1996, both assigned to Procter &Gamble.

[0444] For suitable antidandruff agents see also U.S. Pat. No. 4,948,576to Verdicchio et al, and copending U.S. patent application Ser. No.08/738,211, Attorney docket No 6327 filed on Oct. 25, 1996, Ser. No.08/622,222, Attorney docket No 6041 filed on Mar. 27, 1996, Ser. No.08/975,210, Attorney docket No 5937C, filed Nov. 20, 1997, U.S. Pat.Nos. 4,379,753, 2,694,668, 3,152,046, 4,089,945, 4,885,107, 2,809,971,3,236,733, 3,753,196, 3,761,418, 4,345,080, 4,323,683, 4,379,753 and4,470,982 all of which are incorporated herein by reference.

[0445] Optional Fabric Softener Ingredients

[0446] The fabric softening composition of the invention can alsocontain optional ingredients. A comprehensive list of possible optionalingredients can be found in U.S. Pat. No. 5,747,443, which isincorporated herein by reference.

[0447] Low molecular weight water soluble solvents—can also be used atlevels of from 0% to about 12%, preferably from about 1% to about 10%,more preferably from about 2% to about 8%. The water soluble solventscannot provide a clear product at the same low levels of the principalsolvents described hereinbefore but can provide clear product when theprincipal solvent is not sufficient to provide completely clear product.The presence of these water soluble solvents is therefore highlydesirable. Such solvents include: ethanol; isopropanol; 1,2-propanediol;1,3-propanediol; propylene carbonate; etc. but do not include any of theprincipal solvents (B). These water soluble solvents have a greateraffinity for water in the presence of hydrophobic materials like thesoftener active than the principal solvents.

[0448] Brighteners—The fabric softening compositions herein can alsooptionally contain from about 0.005% to 5% by weight of certain types ofhydrophilic optical brighteners which also provide a dye transferinhibition action. If used, the compositions herein will preferablycomprise from about 0.001% to 1% by weight of such optical brighteners.

[0449] The hydrophilic optical brighteners useful in the presentinvention are those having the structural formula:

[0450] wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

[0451] When in the above formula, R₁ is anilino, R₂ isN-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX® by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the rinse added compositions herein.

[0452] When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX® by Ciba-Geigy Corporation.

[0453] When in the above formula, R₁ is anilino, R₂ is morphilino and Mis a cation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX® by Ciba Geigy Corporation.

[0454] Dispersibility Aids

[0455] Optional Viscosity/Dispersibility Modifiers—Relativelyconcentrated fabric softening compositions containing both saturated andunsaturated diester quaternary ammonium compounds can be prepared thatare stable without the addition of concentration aids. However, thefabric softening compositions of the present invention may requireorganic and/or inorganic concentration aids to go to even higherconcentrations and/or to meet higher stability standards depending onthe other ingredients. These concentration aids which typically can beviscosity modifiers may be needed, or preferred, for ensuring stabilityunder extreme conditions when particular softener active levels areused. The surfactant concentration aids are typically selected from thegroup consisting of (1) single long chain alkyl cationic surfactants;(2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5)mixtures thereof. These aids are described in P&G Copending applicationSer. No. 08/461,207, filed Jun. 5, 1995, Wahl et al., specifically onpage 14, line 12 to page 20, line 12, which is herein incorporated byreference.

[0456] When said dispersibility aids are present, the total level isfrom about 2% to about 25%, preferably from about 3% to about 17%, morepreferably from about 4% to about 15%, and even more preferably from 5%to about 13% by weight of the composition. These materials can either beadded as part of the active softener raw material e.g., the mono-longchain alkyl cationic surfactant and/or the fatty acid which arereactants used to form the biodegradable fabric softener active asdiscussed hereinbefore, or added as a separate component.

[0457] Mono-Alkyl Cationic Quaternary Ammonium Compound—When themono-alkyl cationic quaternary ammonium compound is present, it istypically present at a level of from about 2% to about 25%, preferablyfrom about 3% to about 17%, more preferably from about 4% to about 15%,and even more preferably from 5% to about 13% by weight of thecomposition, the total mono-alkyl cationic quaternary ammonium compoundbeing at least at an effective level.

[0458] Such mono-alkyl cationic quaternary ammonium compounds useful inthe present invention are, preferably, quaternary ammonium salts of thegeneral formula:

[R⁴N+(R⁵)₃]X⁻

[0459] wherein R⁴ is C₈-C₂₂ alkyl or alkenyl group, preferably C₁₀-C₁₈alkyl or alkenyl group; more preferably C₁₀-C₁₄ or C₁₆-C₁₈ alkyl oralkenyl group; each R⁵ is a C₁-C₆ alkyl or substituted alkyl group(e.g., hydroxy alkyl), preferably C₁-C₃ alkyl group, e.g., methyl (mostpreferred), ethyl, propyl, and the like, a benzyl group, hydrogen, apolyethoxylated chain with from about 2 to about 20 oxyethylene units,preferably from about 2.5 to about 13 oxyethylene units, more preferablyfrom about 3 to about 10 oxyethylene units, and mixtures thereof; and X⁻is as defined hereinbefore.

[0460] Especially preferred dispersibility aids are monolauryl trimethylammonium chloride and monotallow trimethyl ammonium chloride availablefrom Witco under the trade name Varisoft® 471 and monooleyl trimethylammonium chloride available from Witco under the tradename Varisoft®417.

[0461] The R⁴ group can also be attached to the cationic nitrogen atomthrough a group containing one, or more, ester, amide, ether, amine,etc., linking groups which can be desirable for increasedconcentratability of fabric softening compositions components. Suchlinking groups are preferably within from about one to about threecarbon atoms of the nitrogen atom.

[0462] Mono-alkyl cationic quaternary ammonium compounds also includeC₈-C₂₂ alkyl choline esters. The preferred dispersibility aids of thistype have the formula:

R¹C(O)—O—CH₂CH₂N⁺(R)₃X⁻

[0463] wherein R¹, R and X⁻ are as defined previously.

[0464] Highly preferred dispersibility aids include C₁₂-C₁₄ coco cholineester and C₁₆-C₁₈ tallow choline ester.

[0465] Suitable biodegradable single-long-chain alkyl dispersibilityaids containing an ester linkage in the long chains are described inU.S. Pat. No. 4,840,738, Hardy and Walley, issued Jun. 20, 1989, saidpatent being incorporated herein by reference.

[0466] When the dispersibility aid comprises alkyl choline esters,preferably the compositions also contain a small amount, preferably fromabout 2% to about 5% by weight of the composition, of organic acid.Organic acids are described in European Patent Application No. 404,471,Machin et al., published on Dec. 27, 1990, supra, which is hereinincorporated by reference. Preferably the organic acid is selected fromthe group consisting of glycolic acid, acetic acid, citric acid, andmixtures thereof.

[0467] Ethoxylated quaternary ammonium compounds which can serve as thedispersibility aid include ethylbis(polyethoxy ethanol)alkylammoniumethyl-sulfate with 17 moles of ethylene oxide, available under the tradename Variquat® 66 from Sherex Chemical Company; polyethylene glycol (15)oleammonium chloride, available under the trade name Ethoquad® 0/25 fromAkzo; and polyethylene glycol (15) cocomonium chloride, available underthe trade name Ethoquad® C/25 from Akzo.

[0468] Although the main function of the dispersibility aid is toincrease the dispersibility of the ester softener, preferably thedispersibility aids of the present invention also have some softeningproperties to boost softening performance of the composition. Therefore,preferably the compositions of the present invention are essentiallyfree of non-nitrogenous ethoxylated nonionic dispersibility aids whichwill decrease the overall softening performance of the compositions.

[0469] Also, quaternary compounds having only a single long alkyl chain,can protect the cationic softener from interacting with anionicsurfactants and/or detergent builders that are carried over into therinse from the wash solution.

[0470] Amine Oxides—Suitable amine oxides include those with one alkylor hydroxyalkyl moiety of about 8 to about 22 carbon atoms, preferablyfrom about 10 to about 18 carbon atoms, more preferably from about 8 toabout 14 carbon atoms, and two alkyl moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups with about 1 to about3 carbon atoms.

[0471] Examples include dimethyloctylamine oxide, diethyldecylamineoxide, bis-(2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamineoxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyldimethylamine oxide.

[0472] Stabilizers—Stabilizers can be present in the fabric softeningcompositions of the present invention. The term “stabilizer,” as usedherein, includes antioxidants and reductive agents. These agents arepresent at a level of from 0% to about 2%, preferably from about 0.01%to about 0.2%, more preferably from about 0.035% to about 0.1% forantioxidants, and more preferably from about 0.01% to about 0.2% forreductive agents. These assure good odor stability under long termstorage conditions. Antioxidants and reductive agent stabilizers areespecially critical for unscented or low scent products (no or lowperfume).

[0473] Examples of antioxidants that can be added to the compositions ofthis invention include a mixture of ascorbic acid, ascorbic palmitate,propyl gallate, available from Eastman Chemical Products, Inc., underthe trade names Tenox® PG and Tenox® S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox®-6; butylated hydroxytoluene, available from UOPProcess Division under the trade name Sustane® BHT; tertiarybutylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ;natural tocopherols, Eastman Chemical Products, Inc., as Tenox®GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,Inc., as BHA; long chain esters (C₈-C₂₂) of gallic acid, e.g., dodecylgallate; Irganox® 1010; Irganox® 1035; Irganox® B 1171; Irganox® 1425;Irganox® 3114; Irganox® 3125; and mixtures thereof; preferably Irganox®3125, Irganox® 1425, Irganox® 3114, and mixtures thereof; morepreferably Irganox® 3125 alone or mixed with citric acid and/or otherchelators such as isopropyl citrate, Dequest® 2010, available fromMonsanto with a chemical name of 1-hydroxyethylidene-1,1-diphosphonicacid (etidronic acid), and Tiron®, available from Kodak with a chemicalname of 4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA®,available from Aldrich with a chemical name ofdiethylenetriaminepentaacetic acid.

[0474] Soil Release Agent—In the present fabric softening compositions,an optional soil release agent can be added. The addition of the soilrelease agent can occur in combination with the premix, in combinationwith the acid/water seat, before or after electrolyte addition, or afterthe final composition is made. The softening composition prepared by theprocess of the present invention herein can contain from 0% to about10%, preferably from 0.2% to about 5%, of a soil release agent. Suitablesoil release agents are described hereinbefore.

[0475] Examples of suitable soil release agents include the commerciallyavailable materials Zelcon 4780® (from Dupont) and Milease T® (fromICI).

[0476] A more complete disclosure of soil release agents is contained inU.S. Pat. No. 4,661,267, Decker, Konig, Straathof, and Gosselink, issuedApr. 28, 1987; U.S. Pat. No. 4,711,730, Gosselink and Diehl, issued Dec.8, 1987; U.S. Pat. No. 4,749,596, Evans, Huntington, Stewart, Wolf, andZimmerer, issued Jun. 7, 1988; U.S. Pat. No. 4,818,569, Trinh,Gosselink, and Rattinger, issued Apr. 4, 1989; U.S. Pat. No. 4,877,896,Maldonado, Trinh, and Gosselink, issued Oct. 31, 1989; U.S. Pat. No.4,956,447, Gosselink et al., issues Sep. 11, 1990; and U.S. Pat. No.4,976,879, Maldonado, Trinh, and Gosselink, issued Dec. 11, 1990, all ofsaid patents being incorporated herein by reference.

[0477] These soil release agents can also act as scum dispersants.

[0478] Scum Dispersant—In the present invention, the premix can becombined with an optional scum dispersant, other than the soil releaseagent, and heated to a temperature at or above the melting point(s) ofthe components.

[0479] The preferred scum dispersants herein are formed by highlyethoxylating hydrophobic materials. The hydrophobic material can be afatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide,quaternary ammonium compound, or the hydrophobic moieties used to formsoil release polymers. The preferred scum dispersants are highlyethoxylated, e.g., more than about 17, preferably more than about 25,more preferably more than about 40, moles of ethylene oxide per moleculeon the average, with the polyethylene oxide portion being from about 76%to about 97%, preferably from about 81% to about 94%, of the totalmolecular weight.

[0480] The level of scum dispersant is sufficient to keep the scum at anacceptable, preferably unnoticeable to the consumer, level under theconditions of use, but not enough to adversely affect softening. Forsome purposes it is desirable that the scum is nonexistent. Depending onthe amount of anionic or nonionic detergent, etc., used in the washcycle of a typical laundering process, the efficiency of the rinsingsteps prior to the introduction of the compositions herein, and thewater hardness, the amount of anionic or nonionic detergent surfactantand detergency builder (especially phosphates and zeolites) entrapped inthe fabric (laundry) will vary. Normally, the minimum amount of scumdispersant should be used to avoid adversely affecting softeningproperties. Typically scum dispersion requires at least about 2%,preferably at least about 4% (at least 6% and preferably at least 10%for maximum scum avoidance) based upon the level of softener active.However, at levels of about 10% (relative to the softener material) ormore, one risks loss of softening efficacy of the product especiallywhen the fabrics contain high proportions of nonionic surfactant whichhas been absorbed during the washing operation.

[0481] Preferred scum dispersants are: Brij 700®; Varonic U-250®;Genapol T-500®, Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.

[0482] Bactericides—Examples of bactericides used in the compositions ofthis invention include glutaraldehyde, formaldehyde,2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located inPhiladelphia, Pa., under the trade name Bronopol®, and a mixture of5-chloro-2-methyl-4-isothiazoline-3-one and2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under thetrade name Kathon about 1 to about 1,000 ppm by weight of the agent.

[0483] Perfume—The present invention can contain any softener compatibleperfume. Suitable perfumes are disclosed in U.S. Pat. No. 5,500,138,Bacon et al., issued Mar. 19, 1996, said patent being incorporatedherein by reference.

[0484] As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants), artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds. Other suitable perfumes are described hereinbefore

[0485] Examples of perfume ingredients useful in the perfumes of thepresent invention compositions include, but are not limited to, hexylcinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexylsalicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol;2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol;3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadien-1-ol;3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one;1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

[0486] Additional examples of fragrance materials include, but are notlimited to, orange oil; lemon oil; grapefruit oil; bergamot oil; cloveoil; dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate;beta-naphthol methylether; methyl-beta-naphthylketone; coumarin;decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate;alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate;Schiffs base of4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methylanthranilate; cyclic ethyleneglycol diester of tridecandioic acid;3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha;ionone beta; petitgrain; methyl cedrylone;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene;ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;16-hydroxy-9-hexadecenoic acid lactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1 b]furan;cedrol; 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexylacetate; patchouli; olibanum resinoid; labdanum; vetivert; copaibabalsam; fir balsam; and condensation products of: hydroxycitronellal andmethyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehydeand indol; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehydeand methyl anthranilate.

[0487] More examples of perfume components are geraniol; geranylacetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol;citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate;tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate;2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate;benzyl salicylate; benzyl benzoate; styrallyl acetate;dimethylbenzylcarbinol; trichloromethylphenylcarbinylmethylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate;vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal;2-methyl-3-(p-isopropylphenyl)-propanal;3-(p-tert-butylphenyl)-propanal;4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal;n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehydedimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile;citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedrylmethylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine;eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methylionones; isomethyl ionones; irones; cis-3-hexenol and esters thereof;indane musk fragrances; tetralin musk fragrances; isochroman muskfragrances; macrocyclic ketones; macrolactone musk fragrances; ethylenebrassylate.

[0488] The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

[0489] Suitable solvents, diluents or carriers for perfumes ingredientsmentioned above are for examples, ethanol, isopropanol, diethyleneglycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethylcitrate, etc. The amount of such solvents, diluents or carriersincorporated in the perfumes is preferably kept to the minimum needed toprovide a homogeneous perfume solution.

[0490] Perfume can be present at a level of from 0% to about 10%,preferably from about 0.1% to about 5%, and more preferably from about0.2% to about 3%, by weight of the finished composition. Fabric softenercompositions of the present invention provide improved fabric perfumedeposition.

[0491] Chelating Agents—The compositions and processes herein canoptionally employ one or more copper and/or nickel chelating agents(“chelators”). Such water-soluble chelating agents can be selected fromthe group consisting of amino carboxylates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof, all as hereinafter defined. The whiteness and/or brightness offabrics are substantially improved or restored by such chelating agentsand the stability of the materials in the compositions are improved.Suitable chelating agents are described hereinbefore.

[0492] Amino carboxylates useful as chelating agents herein includeethylenediaminetetraacetates (EDTA),N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA),ethylenediamine tetraproprionates, ethylenediamine-N,N′-diglutamates,2-hyroxypropylenediamine-N,N′-disuccinates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates(DETPA), and ethanoldiglycines, including their water-soluble salts suchas the alkali metal, ammonium, and substituted ammonium salts thereofand mixtures thereof.

[0493] Amino phosphonates are also suitable for use as chelating agentsin the compositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates),diethylenetriamine-N,N,N′,N″,N″-pentakis(methane phosphonate) (DETMP)and 1-hydroxyethane-1,1-diphosphonate (HEDP). Preferably, these aminophosphonates to not contain alkyl or alkenyl groups with more than about6 carbon atoms.

[0494] The chelating agents are typically used in the present rinseprocess at levels from about 2 ppm to about 25 ppm, for periods from 1minute up to several hours' soaking.

[0495] The preferred EDDS chelator used herein (also known asethylenediamine-N,N′-disuccinate) is the material described in U.S. Pat.No. 4,704,233, cited hereinabove.

[0496] As can be seen from the foregoing, a wide variety of chelatorscan be used herein. Indeed, simple polycarboxylates such as citrate,oxydisuccinate, and the like, can also be used, although such chelatorsare not as effective as the amino carboxylates and phosphonates, on aweight basis. Accordingly, usage levels may be adjusted to take intoaccount differing degrees of chelating effectiveness. The chelatorsherein will preferably have a stability constant (of the fully ionizedchelator) for copper ions of at least about 5, preferably at least about7. Typically, the chelators will comprise from about 0.5% to about 10%,more preferably from about 0.75% to about 5%, by weight of thecompositions herein. Preferred chelators include DETMP, DETPA, NTA, EDDSand mixtures thereof.

[0497] Other Optional Ingredients—The present invention can includeoptional components conventionally used in textile treatmentcompositions, for example: colorants; preservatives; surfactants;anti-shrinkage agents; fabric crisping agents; spotting agents;germicides; fungicides; anti-oxidants such as butylated hydroxy toluene,anti-corrosion agents, and the like.

[0498] Particularly preferred ingredients include water soluble calciumand/or magnesium compounds, which provide additional stability. Thechloride salts are preferred, but acetate, nitrate, etc. salts can beused. The level of said calcium and/or magnesium salts is from 0% toabout 2%, preferably from about 0.05% to about 0.5%, more preferablyfrom about 0.1% to about 0.25%.

[0499] The present invention can also include other compatibleingredients, including those as disclosed in copending applications Ser.Nos. 08/372,068, filed Jan. 12, 1995, Rusche, et al.; Ser. No.08/372,490, filed Jan. 12, 1995, Shaw, et al.; and Ser. No. 08/277,558,filed Jul. 19, 1994, Hartman, et al., incorporated herein by reference.

[0500] Form of the Cleaning Compositions

[0501] The cleaning compositions in accordance with the invention cantake a variety of physical forms including granular, gel, tablet, bar,paste, cream and liquid forms. The form can be dependent upon the enduse of the composition. The compositions include the so-calledconcentrated granular detergent compositions adapted to be added to awashing machine by means of a dispensing device placed in the machinedrum with the soiled fabric load.

[0502] The mean particle size of the components of granular compositionsin accordance with the invention should preferably be such that no morethat 5% of particles are greater than 1.7 mm in diameter and not morethan 5% of particles are less than 0.15 mm in diameter.

[0503] The term mean particle size as defined herein is calculated bysieving a sample of the composition into a number of fractions(typically 5 fractions) on a series of Tyler sieves. The weightfractions thereby obtained are plotted against the aperture size of thesieves. The mean particle size is taken to be the aperture size throughwhich 50% by weight of the sample would pass.

[0504] Certain preferred granular detergent compositions in accordancewith the present invention are the high-density types, now common in themarketplace; these typically have a bulk density of at least 600g/liter, more preferably from 650 g/liter to 1200 g/liter.

[0505] Surfactant Agglomerate Particles

[0506] One of the preferred methods of delivering surfactant in consumerproducts is to make surfactant agglomerate particles, which may take theform of flakes, prills, marumes, noodles, ribbons, but preferably takethe form of granules. A preferred way to process the particles is byagglomerating powders (e.g. aluminosilicate, carbonate) with high activesurfactant pastes and to control the particle size of the resultantagglomerates within specified limits. Such a process involves mixing aneffective amount of powder with a high active surfactant paste in one ormore agglomerators such as a pan agglomerator, a Z-blade mixer or morepreferably an in-line mixer such as those manufactured by Schugi(Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, andGebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used,such as a Lodige CB (Trade Name).

[0507] A high active surfactant paste comprising from 50% by weight to95% by weight, preferably 70% by weight to 85% by weight of surfactantis typically used. The paste may be pumped into the agglomerator at atemperature high enough to maintain a pumpable viscosity, but low enoughto avoid degradation of the anionic surfactants used. An operatingtemperature of the paste of 50° C. to 80° C. is typical.

[0508] Laundry Washing Method

[0509] Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is here meant from 40 g to 300 gof product dissolved or dispersed in a wash solution of volume from 5 to65 liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

[0510] As noted, surfactants are used herein in detergent compositions,preferably in combination with other detersive surfactants, at levelswhich are effective for achieving at least a directional improvement incleaning performance. In the context of a fabric laundry composition,such “usage levels” can vary widely, depending not only on the type andseverity of the soils and stains, but also on the wash watertemperature, the volume of wash water and the type of washing machine.

[0511] In a preferred use aspect a dispensing device is employed in thewashing method. The dispensing device is charged with the detergentproduct, and is used to introduce the product directly into the drum ofthe washing machine before the commencement of the wash cycle. Itsvolume capacity should be such as to be able to contain sufficientdetergent product as would normally be used in the washing method.

[0512] Once the washing machine has been loaded with laundry thedispensing device containing the detergent product is placed inside thedrum. At the commencement of the wash cycle of the washing machine wateris introduced into the drum and the drum periodically rotates. Thedesign of the dispensing device should be such that it permitscontainment of the dry detergent product but then allows release of thisproduct during the wash cycle in response to its agitation as the drumrotates and also as a result of its contact with the wash water.

[0513] Alternatively, the dispensing device may be a flexible container,such as a bag or pouch. The bag may be of fibrous construction coatedwith a water impermeable protective material so as to retain thecontents, such as is disclosed in European published Patent ApplicationNo. 0018678. Alternatively it may be formed of a water-insolublesynthetic polymeric material provided with an edge seal or closuredesigned to rupture in aqueous media as disclosed in European publishedPatent Application Nos. 0011500, 0011501, 0011502, and 0011968. Aconvenient form of water frangible closure comprises a water solubleadhesive disposed along and sealing one edge of a pouch formed of awater impermeable polymeric film such as polyethylene or polypropylene.

[0514] Machine Dishwashing Method

[0515] Any suitable methods for machine washing or cleaning soiledtableware, particularly soiled silverware are envisaged.

[0516] A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 liters,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

[0517] Packaging for the Compositions

[0518] Commercially marketed executions of the bleaching compositionscan be packaged in any suitable container including those constructedfrom paper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European Application No.94921505.7.

[0519] Form of the Skin Care Compositions

[0520] The skin care compositions in accordance with the invention cantake a variety of physical forms including powder, gel, tablet, bar,paste, cream and liquid forms. The form can be dependent upon the enduse of the composition. The skin care composition can also be in atissue, baby wipe, or other similar articles.

[0521] Form of the Personal Cleansing Compositions

[0522] The personal cleansing compositions in accordance with theinvention can take a variety of physical forms including powder, gel,tablet, bar, paste, cream and liquid forms. The form can be dependentupon the end use of the composition.

[0523] Form of the Fabric Softener Compositions

[0524] Solid particulate compositions—The invention also comprises solidparticulate composition comprising:

[0525] from about 50% to about 95%, preferably from about 60% to about90%, of said biodegradable fabric softening active;

[0526] optionally, from 0% to about 30%, preferably from about 3% toabout 15%, of dispersibility modifier; and

[0527] from 0% to about 10% of a pH modifier.

[0528] Optional pH Modifier

[0529] Since the biodegradable ester fabric softener actives aresomewhat labile to hydrolysis, it is preferable to include optional pHmodifiers in the solid particulate fabric softener compositions to whichwater is to be added, to form stable dilute or concentrated liquidsoftener compositions. Said stable liquid fabric softener compositionsshould have a pH (neat) of from about 2 to about 5, preferably fromabout 2 to about 4.5, more preferably from about 2 to about 4.

[0530] The pH can be adjusted by incorporating a solid, water solubleBronsted acid. Examples of suitable Bronsted acids include inorganicmineral acids, such as boric acid, sodium bisulfate, potassiumbisulfate, sodium phosphate monobasic, potassium phosphate monobasic,and mixtures thereof; organic acids, such as citric acid, fumaric acid,maleic acid, malic acid, tannic acid, gluconic acid, glutamic acid,tartaric acid, glycolic acid, chloroacetic acid, phenoxyacetic acid,1,2,3,4-butane tetracarboxylic acid, benzene sulfonic acid, benzenephosphonic acid, ortho-toluene sulfonic acid, para-toluene sulfonicacid, phenol sulfonic acid, naphthalene sulfonic acid, oxalic acid,1,2,4,5-pyromellitic acid, 1,2,4-trimellitic acid, adipic acid, benzoicacid, phenylacetic acid, salicylic acid, succinic acid, and mixturesthereof; and mixtures of mineral inorganic acids and organic acids.Preferred pH modifiers are citric acid, gluconic acid, tartaric acid,1,2,3,4-butane tetracarboxylic acid, malic acid, and mixtures thereof.

[0531] Optionally, materials that can form solid clathrates such ascyclodextrins and/or zeolites, etc., can be used as adjuvants in thesolid particulate composition as host carriers of concentrated liquidacids and/or anhydrides, such as acetic acid, HCl, sulfuric acid,phosphoric acid, nitric acid, carbonic acid, etc. An example of suchsolid clathrates is carbon dioxide adsorbed in zeolite A, as disclosedin U.S. Pat. No. 3,888,998, Whyte and Samps, issued Jun. 10, 1975 andU.S. Pat. No. 4,007,134, Liepe and Japikse, issued Feb. 8, 1977, both ofsaid patents being incorporated herein by reference. Examples ofinclusion complexes of phosphoric acid, sulfuric acid, and nitric acid,and process for their preparation are disclosed in U.S. Pat. No.4,365,061, issued Dec. 21, 1982 to Szejtli et al., said patent beingincorporated herein by reference.

[0532] When used, the pH modifier is typically used at a level of fromabout 0.01% to about 10%, preferably from about 0.1% to about 5%, byweight of the composition.

[0533] Preparation of Solid Particulate Granular Fabric Softener

[0534] The granules can be formed by preparing a melt, solidifying it bycooling, and then grinding and sieving to the desired size. In athree-component mixture, e.g., nonionic surfactant, single-long-chaincationic, and DEQA, it is more preferred, when forming the granules, topre-mix the nonionic surfactant and the more soluble single-long-chainalkyl cationic compound before mixing in a melt of the diesterquaternary ammonium cationic compound.

[0535] It is highly preferred that the primary particles of the granuleshave a diameter of from about 50 to about 1,000, preferably from about50 to about 400, more preferably from about 50 to about 200, microns.The granules can comprise smaller and larger particles, but preferablyfrom about 85% to about 95%, more preferably from about 95% to about100%, are within the indicated ranges. Smaller and larger particles donot provide optimum emulsions/dispersions when added to water. Othermethods of preparing the primary particles can be used including spraycooling of the melt. The primary particles can be agglomerated to form adust-free, non-tacky, free-flowing powder. The agglomeration can takeplace in a conventional agglomeration unit (i.e., Zig-Zag Blender,Lodige) by means of a water-soluble binder. Examples of water-solublebinders useful in the above agglomeration process include glycerol,polyethylene glycols, polymers such as PVA, polyacrylates, and naturalpolymers such as sugars.

[0536] The flowability of the granules can be improved by treating thesurface of the granules with flow improvers such as clay, silica orzeolite particles, water-soluble inorganic salts, starch, etc.

[0537] Method of Use

[0538] Water can be added to the particulate, solid, granularcompositions to form dilute or concentrated liquid softener compositionsfor later addition to the rinse cycle of the laundry process with aconcentration of said biodegradable cationic softening compound of fromabout 0.5% to about 50%, preferably from about 1% to about 35%, morepreferably from about 4% to about 32%. The particulate, rinse-addedsolid composition (1) can also be used directly in the rinse bath toprovide adequate usage concentration (e.g., from about 10 to about 1,000ppm, preferably from about 50 to about 500 ppm, of total softener activeingredient). The liquid compositions can be added to the rinse toprovide the same usage concentrations.

[0539] The water temperature for preparation should be from about 20° C.to about 90° C., preferably from about 25° C. to about 80° C.Single-long-chain alkyl cationic surfactants as theviscosity/dispersibility modifier at a level of from 0% to about 15%,preferably from about 3% to about 15%, more preferably from about 5% toabout 15%, by weight of the composition, are preferred for the solidcomposition. Nonionic surfactants at a level of from about 5% to about20%, preferably from about 8% to about 15%, as well as mixtures of theseagents can also serve effectively as the viscosity/dispersibilitymodifier.

[0540] The emulsified/dispersed particles, formed when the said granulesare added to water to form aqueous concentrates, typically have anaverage particle size of less than about 10 microns, preferably lessthan about 2 microns, and more preferably from about 0.2 to about 2microns, in order that effective deposition onto fabrics is achieved.The term “average particle size,” in the context of this specification,means a number average particle size, i.e., more than 50% of theparticles have a diameter less than the specified size.

[0541] Particle size for the emulsified/dispersed particles isdetermined using, e.g., a Malvern particle size analyzer.

[0542] Depending upon the particular selection of nonionic and cationicsurfactant, it may be desirable in certain cases, when using the solidsto prepare the liquid, to employ an efficient means for dispersing andemulsifying the particles (e.g., blender).

[0543] Solid particulate compositions used to make liquid compositionscan, optionally, contain electrolytes, perfume, antifoam agents, flowaids (e.g., silica), dye, preservatives, and/or other optionalingredients described hereinbefore.

[0544] The benefits of adding water to the particulate solid compositionto form aqueous compositions to be added later to the rinse bath includethe ability to transport less weight thereby making shipping moreeconomical, and the ability to form liquid compositions similar to thosethat are normally sold to consumers, e.g., those that are describedherein, with lower energy input (i.e., less shear and/or lowertemperature). Furthermore, the particulate granular solid fabricsoftener compositions, when sold directly to the consumers, have lesspackaging requirements and smaller, more disposable containers. Theconsumers will then add the compositions to available, more permanent,containers, and add water to pre-dilute the compositions, which are thenready for use in the rinse bath, just like the liquid compositionsherein. The liquid form is easier to handle, since it simplifiesmeasuring and dispensing.

[0545] Dryer Activated Compositions—The present invention also relatesto improved solid dryer-activated fabric softener compositions which areeither incorporated into articles of manufacture, e.g., on a substrate,or, are in the form of particles similar to those disclosed above.(including, where appropriate, agglomerates, pellets, and tablets ofsaid particles). Such compositions typically contain from about 10% toabout 95% of fabric softening agent.

[0546] Substrate Articles—In preferred embodiments, the presentinvention encompasses articles of manufacture. Representative articlesare those that are adapted for use to provide unique perfume benefitsand to soften fabrics in an automatic laundry dryer, of the typesdisclosed in U.S. Pat. No. 3,989,631 Marsan, issued Nov. 2, 1976; U.S.Pat. No. 4,055,248, Marsan, issued Oct. 25, 1977; U.S. Pat. No.4,073,996, Bedenk et al., issued Feb. 14, 1978; U.S. Pat. No. 4,022,938,Zaki et al., issued May 10, 1977; U.S. Pat. No. 4,764,289, Trinh, issuedAug. 16, 1988; U.S. Pat. No. 4,808,086, Evans et al., issued Feb. 28,1989; U.S. Pat. No. 4,103,047, Zaki et al., issued Jul. 25, 1978; U.S.Pat. No. 3,736,668, Dillarstone, issued Jun. 5, 1973; U.S. Pat. No.3,701,202, Compa et al., issued Oct. 31,1972; U.S. Pat. No. 3,634,947,Furgal, issued Jan. 18, 1972; U.S. Pat. No. 3,633,538, Hoeflin, issuedJan. 11, 1972; and U.S. Pat. No. 3,435,537, Rumsey, issued Apr. 1, 1969;and U.S. Pat. No. 4,000,340, Murphy et al., issued Dec. 28, 1976, all ofsaid patents being incorporated herein by reference.

[0547] Typical articles of manufacture of this type include articlescomprising:

[0548] I. a fabric conditioning composition comprising from about 30% toabout 95% of normally solid, dryer softenable fabric softening agentcomprising said biodegradable fabric softening active; and

[0549] II. a dispensing means which provides for release of an effectiveamount of said composition including an effective amount of ii,sufficient to provide odor control, to fabrics in an automatic laundrydryer at automatic laundry dryer operating temperatures, e.g., fromabout 35° C. to 115° C.

[0550] When the dispensing means is a flexible substrate, e.g., in sheetconfiguration, the fabric conditioning composition is releasably affixedon the substrate to provide a weight ratio of conditioning compositionto dry substrate ranging from about 10:1 to about 0.5:1, preferably fromabout 5:1 to about 1:1.

[0551] The solid fabric softener compositions herein can includecationic and nonionic fabric softener actives used in combination witheach other.

[0552] In the following Examples, the abbreviations for the variousingredients used for the compositions have the following meanings. MBFAMid-chain branched fatty acid MBFS Salt of Mid-chain branched fatty acidMES Alkyl methyl ester sulfonate SAS Secondary alkyl sulfate NaPS Sodiumparaffin sulfonate C45AS Sodium C₁₄-C₁₅ linear alkyl sulfate CxyASSodium C_(1x)-C_(1y) alkyl sulfate (or other salt if specified) CxyEzSSodium C_(1x)-C_(1y) alkyl sulfate condensed LAS Sodium linear alkylbenzene sulfonate Citric acid Anhydrous citric acid LMFAA C12-14 alkylN-methyl glucamide CxyFA C_(1x)-C_(1y) fatty acid CxyEz A C_(1x-1y)branched primary alcohol condensed with an average of z moles ofethylene oxide Carbonate Anhydrous sodium carbonate with a particle sizebetween 200 μm and 900 μm Citrate Tri-sodium citrate dihydrate ofactivity 86.4% with a particle size distribution between 425 μm and 850μm TFAA C16-18 alkyl N-methyl glucamide Fatty Acid (C12/14) C12-C14fatty acid Fatty Acid (TPK) Topped palm kernel fatty acid Fatty Acid(RPS) Rapeseed fatty acid Borax Na tetraborate decahydrate PAAPolyacrylic Acid (mw = 4500) PEG Polyethylene glycol (mw = 4600) with zmoles of ethylene oxide (or other salt if specified) CxyEz A C_(1x-1y)branched primary alcohol condensed with an average of z moles ofethylene oxide AQA R₂.N⁺(CH₃)_(x)((C₂H₄O)yH)z with R₂ = C₈-C₁₈ x + z =3, x = 0 to 3, z = 0 to 3, y = 1 to 15. STPP Anhydrous sodiumtripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formulaNa₁₂(AlO₂SiO₂)₁₂.27H₂O having a primary particle size in the range from0.1 to 10 micrometers NaSKS-6 Crystalline layered silicate of formula δ—Na₂Si₂O₅ Carbonate Anhydrous sodium carbonate with a particle sizebetween 200 μm and 900 μm Bicarbonate Anhydrous sodium bicarbonate witha particle size distribution between 400 μm and 1200 μm SilicateAmorphous Sodium Silicate (SiO₂:Na₂O; 2.0 ratio) Sulfate Anhydroussodium sulfate PAE ethoxylated tetraethylene pentamine PIE ethoxylatedpolyethylene imine PAEC methyl quaternized ethoxylated dihexylenetriamine MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecularweight about 70,000. CMC Sodium carboxymethyl cellulose ProteaseProteolytic enzyme of activity 4 KNPU/g sold by NOVO Industries A/Sunder the tradename Savinase Cellulase Cellulytic enzyme of activity1000 CEVU/g sold by NOVO Industries A/S under the tradename CarezymeAmylase Amylolytic enzyme of activity 60 KNU/g sold by NOVO IndustriesA/S under the tradename Termamyl 60T Lipase Lipolytic enzyme of activity100 kLU/g sold by NOVO Industries A/S under the tradename Lipolase PB1Anhydrous sodium perborate bleach of nominal formula NaBO₂.H₂O₂Percarbonate Sodium Percarbonate of nominal formula 2Na₂CO₃.3H₂O₂ NaDCCSodium dichloroisocyanurate NOBS Nonanoyloxybenzene sulfonate, sodiumsalt TAED Tetraacetylethylenediamine DTPMP Diethylene triamine penta(methylene phosphonate), marketed by Monsanto under Trade name Dequest2060 Photoactivated bleach Sulfonated Zinc Phthalocyanine bleachencapsulated in dextrin soluble polymer Brightener 1 Disodium4,4′-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium4,4′-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino)stilbene-2:2′-disulfonate. HEDP 1,1-hydroxyethanediphosphonic acid SRP 1 Sulfobenzoyl end capped esters with oxyethyleneoxy and terephthaloyl backbone SRP 2 sulfonated ethoxylatedterephthalate polymer SRP 3 methyl capped ethoxylated terephthalatepolymer Silicone antifoam Polydimethylsiloxane foam controller withsiloxane-oxyalkylene copolymer as dispersing agent with a ratio of saidfoam controller to said dispersing agent of 10:1 to 100:1. DTPADiethylene triamine pentaacetic acid Endolase Endoglunase enzyme ofactivity 3000 CEVU/g sold by NOVO Industries A/S MEA Monoethanolamine PGPropanediol BPP Butoxy-propoxy-propanol EtOH Ethanol NaOH Solution ofsodium hydroxide NaTS Sodium toluene sulfonate TFAA C16-18 alkylN-methyl glucamide LMFAA C12-14 alkyl N-methyl glucamide APA C8-C10amido propyl dimethyl amine Isofol 16 Condea trademark for C16 (average)Guerbet alcohols

[0553] In the following Examples all levels are quoted as % by weight ofthe composition. The following examples are illustrative of the presentinvention, but are not meant to limit or otherwise define its scope. Allparts, percentages and ratios used herein are expressed as percentweight unless otherwise specified.

EXAMPLE I

[0554] The following laundry detergent compositions A to D are preparedin accord with the invention: A B C D MBFS¹ 2 4.0 4.0 8.0 C45AS 6 4.02.8 — LAS — — 1.2 — C25E3 3.4 3.4 3.4 3.4 AQA 0.4 0.5 0.6 0.8 Zeolite A18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 Silicate 1.4 1.4 1.43.0 Sulfate 26.1 26.1 26.1 26.1 PB1 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.5 1.5DTPMP 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.3 0.3 Protease 0.26 0.26 0.260.26 Amylase 0.1 0.1 0.1 0.1 MA/AA 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2Photoactivated 15 ppm 15 ppm 15 ppm 15 ppm bleach Brightener 1 0.09 0.090.09 0.09 Perfume 0.3 0.3 0.3 0.3 Silicone 0.5 0.5 0.5 0.5 antifoamMisc/minors to 100% Density in 850 850 850 850 g/liter

EXAMPLE II

[0555] The following laundry detergent compositions E to I are preparedin accord with the invention: E F G H I MBFS¹ 22 16.5 11 1-5.5 10-25  Any Combination of: 0 1-5.5 11 16.5 0-5   C45 AS C45E1S LAS C16 SASC14-17 NaPS C14-18 MES AQA 0-2   0-2   0-2   0-2   0-4   C23E6.5 orC45E7 1.5 1.5 1.5 1.5 0-4   Zeolite A 27.8 27.8 27.8 27.8 20-30   PAA2.3 2.3 2.3 2.3 0-5   Carbonate 27.3 27.3 27.3 27.3 20-30   Silicate 0.60.6 0.6 0.6 0-2   PB1 1.0 1.0 1.0 1.0 0-3   Protease 0-0.5 0-0.5 0-0.50-0.5 0-0.5 Cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.5 Amylase 0-0.5 0-0.50-0.5 0-0.5 0-1   SRP 1 0.4 0.4 0.4 0.4 0-1   Brightener 1 or 2 0.2 0.20.2 0.2 0-0.3 PEG 1.6 1.6 1.6 1.6 0-2   Sulfate 5.5 5.5 5.5 5.5 0-6  Silicone Antifoam 0.42 0.42 0.42 0.42 0-0.5 Moisture & Minors —Balance—Density (g/L) 663 663 663 663 600-700  

EXAMPLE III

[0556] The following laundry detergent compositions J to N are preparedin accord with the invention: J K L M N MBFS¹ 16.5 12.5 8.5 4 1-25  AnyCombination of: 0-6 10 14 18.5 0-20  C45 AS C45E1S LAS C16 SAS C14-17NaPS C14-18 MES AQA 0-2 0-2 0-2 0-2 0-4   TFAA 1.6 1.6 1.6 1.6 0-4  C24E3, C23E6.5 5 5 5 5 0-6   Zeolite A 15 15 15 15 10-30   NaSKS-6 11 1111 11 5-15  Citrate 3 3 3 3 0-8   MA/AA 4.8 4.8 4.8 4.8 0-8   HEDP 0.50.5 0.5 0.5 0-1   Carbonate 8.5 8.5 8.5 8.5 0-15  Percarbonate or PB120.7 20.7 20.7 20.7 0-25  TAED 4.8 4.8 4.8 4.8 0-8   Protease 0.9 0.90.9 0.9 0-1   Lipase 0.15 0.15 0.15 0.15 0-0.3 Cellulase 0.26 0.26 0.260.26 0-0.5 Amylase 0.36 0.36 0.36 0.36 0-0.5 SRP 1 0.2 0.2 0.2 0.2 0-0.5Brightener 1 or 2 0.2 0.2 0.2 0.2 0-0.4 Sulfate 2.3 2.3 2.3 2.3 0-25 Silicone Antifoam 0.4 0.4 0.4 0-1   Moisture & Minors —Balance— Density(g/L) 850 850 850 850

EXAMPLE IV

[0557] The following laundry detergent compositions 0 to T are preparedin accord with the invention: O P Q R S T MBFS¹ 32 24 16 8 4 1-35 AnyCombination of: 0 8 16 24 28 0-35 C45 AS C45E1S LAS C16 SAS C14-17 NaPSC14-18 MES C23E6.5 or C45E7 3.6 3.6 3.6 3.6 3.6 0-6 AQA 0-1   0-1  0-1   0-1   0-1   0-4 Zeolite A 9.0 9.0 9.0 9.0 9.0 0-20 PAA or MA/AA7.0 7.0 7.0 7.0 7.0 0-10 Carbonate 18.4 18.4 18.4 18.4 18.4 5-25Silicate 11.3 11.3 11.3 11.3 11.3 5-25 PB1 3.9 3.9 3.9 3.9 3.9 1-6 NOBS4.1 4.1 4.1 4.1 4.1 0-6 Protease 0.9 0.9 0.9 0.9 0.9 0-1.3 Amylase 0-0.50-0.5 0-0.5 0-0.5 0-0.5 0-0.5 Cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.30-0.3 SRP1 0.5 0.5 0.5 0.5 0.5 0-1 Brightener 1 or 2 0.3 0.3 0.3 0.3 0.30-0.5 PEG 0.2 0.2 0.2 0.2 0.2 0-0.5 Sulfate 5.1 5.1 5.1 5.1 5.1 0-10Silicone Antifoam 0.2 0.2 0.2 0.2 0.2 0-0.5 Moisture & Minors —Balance—Density (g/L) 810 810 810 810 810 810

EXAMPLE V

[0558] The following high density detergent formulations U to X,according to the present invention, are prepared: U V W X AgglomerateC45AS 11.0 7.0 4 14.0 MBFS¹ 3.0 10.0 17.0 3.0 Zeolite A 15.0 12.0 10.010.0 Carbonate 4.0 4.0 4.0 8.0 PAA or MA/AA 4.0 4.0 4.0 2.0 CMC 0.5 0.50.5 0.5 DTPMP 0.4 0.4 0.4 0.4 Spray On C23E6.5 5.0 5.0 5.0 5.0 Perfume0.5 0.5 0.5 0.5 Dry Adds C45AS 6.0 6.0 3.0 3.0 HEDP 0.5 0.5 0.5 0.3SKS-6 13.0 13.0 13.0 6.0 Citrate 3.0 3.0 3.0 1.0 TAED 5.0 5.0 5.0 7.0Percarbonate 20.0 20.0 20.0 20.0 SRP 1 0.3 0.3 0.3 0.3 Protease 1.4 1.41.4 1.4 Lipase 0.4 0.4 0.4 0.4 Cellulase 0.6 0.6 0.6 0.6 Amylase 0.6 0.60.6 0.6 Silicone antifoam 5.0 5.0 5.0 5.0 Brightener 1 0.2 0.2 0.2 0.2Brightener 2 0.2 0.2 0.2 — Balance (Water/Miscellaneous) 100 100 100 100Density (g/liter) 850 850 850 850

EXAMPLE VI

[0559] The following laundry detergent compositions Y to BB suitable forhand-washing soiled fabrics are prepared in accord with the invention: YZ AA BB MBFS¹  5 10 18 22 LAS 20 10 11 — STPP 15 30 11 28 Carbonate 15 820 15 Silicates 15 10 15 10 Protease  0 0 0.3 0.3 Perborate  0 0 0 10Sodium Chloride 25 15 20 10 Brightener, perfume 0-0.3 0.2 0.2 0.2Moisture & Minors² —Balance—

EXAMPLE VII

[0560] The following laundry detergent compositions CC to FF suitablefor hand-washing soiled fabrics are prepared in accord with theinvention: CC DD EE FF MBFS¹ 22 16 11 1-6 Any Combination of:  0 0-5  5-15  10-20   C45 AS C45E1S C45E3S LAS AQA 0-5   0-1   0-5   0-3   AnyCombination of: 0-2   0-4   0-2   0-2   C23E65 C45E7 STPP 5-45  5-45 5-45  5-45  PAA 0-2   0-2   0-2   0-2   CMC 0-0.5 0-0.5 0-0.5 0-0.5Protease 0-0.5 0-0.5 0-0.5 0-0.5 Cellulase 0-0.3 0-0.3 0-0.3 0-0.3Amylase 0-0.5 0-0.5 0-0.5 0-0.5 SRP 0-0.5 0.4 0-0.5 0-0.5 Brightener,perfume 0-0.3 0-0.2 0-0.3 0-0.2 Photobleach 0-0.1 0-0.1 0-0.1 0-0.1Carbonate 15 10 20 15 Silicate  7 15 10  8 Sulfate  5 5  5  5 Moisture &Minors² —Balance—

EXAMPLE VIII

[0561] Light-duty liquid dishwashing detergent compositions comprisingthe mid-chain branched soaps of the present claims are prepared: Wt. %Wt. % Wt. % Wt. % Ingredient GG HH II JJ C23E0.6S 25 20 15 0 C23E9 1 1 11 MBFS¹ 5 10 15 30 LMFAA 4 4 4 4 Coconut amine oxide 4 4 4 4 EO/PO BlockCo-polymer— 0.5 0.5 0.5 0.5 Tetronic ® 704 EtOH 6 6 6 6 Calcium xylenesulfonate 5 5 5 5 Magnesium⁺⁺ (added as chloride) 3.0 3.0 3.0 3.0 Water,thickeners and minors to 100% to 100% to 100% to 100% pH @ 10% (as made)7.5 7.5 7.5 7.5

EXAMPLE IX

[0562] This example illustrates the preparation and performanceadvantages of the mid-chain branched fatty acid containing non-aqueousliquid detergent compositions of the instant invention. Such examples,however, are not necessarily meant to limit or otherwise define thescope of the invention herein. All parts, percentages and ratios usedherein are expressed as percent weight unless otherwise specified.

Preparation of LAS Powder for Use as a Structurant

[0563] Sodium C₁₂ linear alkyl benzene sulfonate (NaLAS) is processedinto a powder containing two phases. One of these phases is soluble inthe non-aqueous liquid detergent compositions herein and the other phaseis insoluble. It is the insoluble fraction which serves to add structureand particle suspending capability to the non-aqueous phase of thecompositions herein.

[0564] NaLAS powder is produced by taking a slurry of NaLAS in water(approximately 40-50% active) combined with dissolved sodium sulfate(3-15%) and hydrotrope, sodium sulfosuccinate (1-3%). The hydrotrope andsulfate are used to improve the characteristics of the dry powder. Adrum dryer is used to dry the slurry into a flake. When the NaLAS isdried with the sodium sulfate, two distinct phases are created withinthe flake. The insoluble phase creates a network structure of aggregatesmall particles (0.4-2 um) which allows the finished non-aqueousdetergent product to stably suspend solids.

[0565] The NaLAS powder prepared according to this example has thefollowing makeup shown in Table I. TABLE I LAS Powder Component Wt. %NaLAS 85% Sulfate 11% Sulfosuccinate  2% Water 2.5%  Unreacted, etc.balance to 100%  % insoluble LAS 17% # of phase (via X-ray diffraction) 2   

[0566] TABLE II Non-aqueous based heavy duty liquid laundry detergentcompositions (KK to OO) which comprise the mid-chain branched acids ofthe present invention are presented below. Non-Aqueous Liquid DetergentComposition with Bleach Wt % Wt % Wt % Wt % Wt % Component KK LL MM NNOO LAS, From Above 16 13 8 8 2 MBFA¹ 22 25 28 30 34 BPP 19 19 19 19 19Citrate 3 3 3 3 3 Bleach activator 5.9 5.9 5.9 5.9 5.9 Carbonate 9 9 9 99 MA/AA 3 3 3 3 3 Colored speckles 0.4 0.4 0.4 0.4 0.4 EDDS 1 1 1 1 1Cellulase Prills 0.1 0.1 0.1 0.1 0.1 Amylase Prills 0.4 0.4 0.4 0.4 0.4Ethoxylated diamine quat 1.3 1.3 1.3 1.3 1.3 Perborate 15 15 15 15 15Optionals including: balance balance balance balance balance brightener,colorant, perfume, thickener, suds suppressor, colored speckles etc.100% 100% 100% 100% 100%

[0567] The resulting Table II composition is a stable, anhydrousheavy-duty liquid laundry detergent which provides excellent stain andsoil removal performance when used in normal fabric launderingoperations.

EXAMPLE X

[0568] Aqueous based heavy duty liquid laundry detergent compositions PPto TT which comprise the mid-chain branched soaps of the presentinvention are presented below. Ingredient PP QQ RR SS TT MBFS 10 8 6 4 2Na C25AE1.8S 10 12 14 16 18 C23E9 2 2 2 2 2 LMFAA 5 5 5 5 0 Citric acidbuilder 3 3 3 3 3 Fatty acid builder 0 1 2 4 5 PAE 1 1 1.2 1.2 0.5 PG 88 8 8 4.5 EtOH 4 4 4 4 2 Boric acid 3.5 3.5 3.5 3.5 2 Sodium Cumene 3 33 3 0 Sulfonate pH = 8.0 8.0 8.0 8.0 7.0 Enzymes, dyes, water balancebalance balance balance balance 100% 100% 100% 100% 100%

EXAMPLE XI

[0569] The following aqueous liquid laundry detergent compositions UU toYY are prepared in accord with the invention: UU VV WW XX YY MBFS 1-7  7-12  12-17   17-22   1-35  Any combination of: 15-21   10-15   5-10 0-5   0-25  C25 AExS * Na (x = 1.8-2.5) C25 AS (linear to high 2-alkyl)C14-17 NaPS C12-16 SAS C18 1,4 disulfate LAS C12-16 MES LMFAA 0-3.50-3.5 0-3.5 0-3.5 0-8   C23E9 or C23E6.5 0-2   0-2   0-2   0-2   0-8  APA 0.5 0.5 0.5 0.5 0.5-2   Citric Acid 5 5 3 3 0-8   Fatty Acid (TPK or4 3 2 1 0-14  C12/14) EtOH 4 4 4 4 0-8   PG 6 6 6 6 0-10  MEA 1 1 1 10-3   NaOH 3 3 3 3 0-7   Na TS 2.3 2.3 2.3 2.3 0-4   Na formate 0.1 0.10.1 0.1 0-1   Borax 2.5 2.5 2.5 2.5 0-5   Protease 0.9 0.9 0.9 0.9 0-1.3Lipase 0.06 0.06 0.06 0.06 0-0.3 Amylase 0.15 0.15 0.15 0.15 0-0.4Cellulase 0.05 0.05 0.05 0.05 0-0.2 PAE 0-0.6 0-0.6 0-0.6 0-0.6 0-2.5PIE 1.2 1.2 1.2 1.2 0-2.5 PAEC 0-0.4 0-0.4 0-0.4 0-0.4 0-2   SRP 2 0.20.2 0.2 0.2 0-0.5 Brightener 1 or 2 0.15 0.15 0.15 0.15 0-0.5 Siliconeantifoam 0.12 0.12 0.12 0.12 0-0.3 Fumed Silica 0.0015 0.0015 0.00150.0015  0-0.003 Perfume 0.3 0.3 0.3 0.3 0-0.6 Dye 0.0013 0.0013 0.00130.0013  0-0.003 Moisture/minors Balance Balance Balance Balance BalanceProduct pH (10% in 7.7 7.7 7.7 7.7 6-9.5 DI water)

EXAMPLE XII Clear Fabric Softener Compositions with Various FabricSoftener Levels and Solvent Systems

[0570] Component (Wt %) A1 B1 C1 D1 E1 F1 G1 H1 I1 TEA Di- 30 35 30 3030 35 30 35 30 ester Quat¹ Ethanol(from 2.47 2.88 2.47 2.47 2.47 2.882.47 2.88 2.47 active) Hexylene 2.7 3.1 2.7 2.7 2.7 3.1 2.7 3.1 2.7Glycol(from active) TMPD 4 5 — 5 5 — — — 5.5 Hexylene — — 6 — — 10 — 2 —Glycol 2-Ethyl- — — — — — — 6 — — 1,3- Hexanediol Neodol 5 6 4 6 6 5 5 56 91-8 Pluronic 1 1 1 1 1 1 1 1 1 L-35O HCl 0-0.25 0-0.25 0-0.25 0-0.250-0.25 0-0.25 0-0.25 0-0.25 0-0.25 MgCl2 1.75 1.75 2.00 1.75 1.75 2.201.50 1.75 1.75 Perfume 2.2 2.5 2.5 2 2.5 3 2 2 2 DTPA 0.01 0.01 0.010.01 0.01 0.01 0.01 0.01 0.01 Blue 0.0003 0.0003 0.0003 0.0003 0.00030.0003 0.0003 0.0003 0.0003 Dye Deionized Bal. Bal. Bal. Bal. Bal. Bal.Bal. Bal. Bal. Water & Minors

EXAMPLE XIII Clear Fabric Softener Compositions with Low Solvent Levelsand Various Principal Solvents.

[0571] Component Wt % J1 K1 L1 M1 N1 O1 TEA Di-ester 30 30 45 40 45 30Quat¹. Ethanol from 2.47 2.47 3.71 3.29 3.71 2.47 softener activeHexylene Glycol 2.65 2.65 3.97 3.53 3.97 2.65 from softener activePrincipal Solvent: TMPD 5 5 — — — 4 1,2-Hexanediol — — 1 — — —1,2-Pentanediol — — — 1 — — 1,2-Butanediol — — — — 3 — Phase Stabilizer:Neodol 91-8 5 5 — — — 5 Rewopal C6 — — 2.9 2.9 2.9 — Pluronic L35 1 10.5 1 — 1 MgCl2 1.75 — — — — 1.75 CaCl2 — 1.75 — — — — Perfume 1.8 2.01.5 1.5 1.5 2.2 De-ionized Water & Bal. Bal. Bal. Bal. Bal. Bal. minors

[0572] Clear Fabric Softening Compositions with 45% Fabric SoftenerActive and Various Electrolytes and Solvent Systems. Component Wt % P1Q1 R1 S1 T1 U1 V1 W1 TEA Di-ester 45 45 45 45 45 45 45 45 Quat.¹ Ethanol(from 7 — 3.71 3.71 3.71 3.71 3.71 3.71 active) Hexylene — 3.97 3.973.97 3.97 3.97 3.97 3.97 Glycol (from active) Hexylene — 2.03 — — — — —— Glycol Pinacol — — 3 — — — — — Neopentyl — — — 3 — — — — GlycolIsopropanol — — — — — — 3 — Butyl Carbitol — — — — — — — 3.1 1,5- — — —— — 3 — — Hexanediol Rewopal C6 3 3 3 3 3 3 3 3.6 Electrolyte KCl CaCl2KCl CaCl2 K Citrate K Citrate CaCl2 CaCl2 % of 1 1 1 1 2 2 1 1.2Electrolyte Perfume 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2 De-ionized Bal. Bal.Bal. Bal. Bal. Bal. Bal. Bal. Water

[0573] Clear Fabric Softening Compositions with Hexylene Glycol asPrincipal Solvent. Component Wt % X1 Y1 Z1 A2 B2 C2 D2 E2 F2 G2 H2 TEADi- 45 45 45 45 45 30 28 32 32 36 36 ester Quat.¹ Ethanol 3.7 3.7 3.73.7 3.7 2.5 2.3 2.6 2.6 3.3 3.3 (from active) Hexylene 4 4 4 4 4 2.7 2.52.8 2.8 — — Glycol (from active) Hexylene 3 6 9 7.3 3 9 3 3.3 6.1 6.56.5 Glycol Rewopal 3.5 2.5 1.5 3.1 2.9 3 — — — 1.8 1.8 C6 Neodol 91-8 —— — — — — 3.1 3.0 4.9 — — CaCl2 1.1 1.1 0.8 2 1 0.95 2.1 2 1 — 1.2Sodium — — — — — — — — — 1 — Cumene Sulfonate Perfume 2.0 2.0 2.0 2.01.5 1.5 1.0 1.1 3.2 1.2 1.2 De-ionized Bal. Bal. Bal. Bal. Bal. Bal.Bal. Bal. Bal. Bal. Bal. Water

EXAMPLE XIV Dispersion Examples

[0574] The compositions of Example XIV are made at ambient temperatureby the following process:

[0575] 1. Prepare the water seat containing HCl.

[0576] 2. Separately, mix perfume and Tenox antioxidant to the diestersoftener active.

[0577] 3. Add the diester active blend into the water seat with mixing.

[0578] 4. Add about 10-20% of the CaCl₂ solution at approximatelyhalfway through the diester addition.

[0579] 5. Add the remainder of the CaCl₂ solution after the diesteraddition is complete with mixing. Ingredients Wt. % I2 J2 K2 L2 M2 N2DEQA2 (85% 18 — 15 — — — active in ethanol) DEQA8 (85% — 18 — 12 — —active in ethanol) DEQA10 9.2 9.2 15 12 — — (85% active in ethanol)DEQA24 — — — — — 20.8 (85% active in ethanol) DEQA25 — — — — — 28 (85%active in ethanol) Perfume 1.35 1.35 1.35 1.35 1.35 1.35 Tenox 6 0.040.04 0.04 0.04 0.04 0.04 CaCl2 (25% 2 2 2 2 2 2 solution) HCl 1N 0.300.30 0.30 0.30 0.30 0.30 Distilled Bal. Bal. Bal. Bal. Bal. Bal. Water

[0580] The above Examples show dispersion compositions with goodstability and performance.

What is claimed is:
 1. A composition of matter comprising branchedcarboxylic acids having 16 carbon atoms in total chain length, and thelower alkyl esters, the stereoisomers, or the salts thereof, whereinsaid composition of matter comprises: (a) 14-methylpentadecanoic acid;(b) 2,5-, 2,7-, 2,9-, 2,11-, 2,12- and 2,13-dimethyltetradecanoic acid;and mixtures thereof; (c) 3,4-, 3,6-, 3,8-, 3,10-, 3,12-, 3,13-, 4,5-,4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 5,6-, 5,8-, 5,10-, 5,11-,5,12-, 5,13-, 6,7-, 6,8-, 6,9-, 6,11-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-,8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 9,10-, 9,11-, 9,12-, 10,11-, 10,12-,11,12-, 11,13- and 12,13-, dimethyltetradecanoic acid; and mixturesthereof; (d) 3-, 4-, 5-, 6-, 7-, 8-, 9- and 11-methyl-2-ethyltridecanoicacid; and mixtures thereof; (e) 3-, 5-, 7-, 8-, 9-, 10-, 11- and12-ethyltetradecanoic acid; and mixtures thereof; (f) 3-, 4-, 5-, 6-,7-, 8-, 9- and 10-propyltridecanoic acid; and mixtures thereof; (g)3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 4,5-, 4,7-, 4,8-,4,9-, 4,10-, 4,11-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-, 6,7-, 6,9-,6,11-, 7,8-, 7,9-, 7,10-, 7,11-, 8,9-, 8,10-, 8,11-, 9,10-, 9,11- and10,11-dimethyl-2-ethyldodecanoic acid; and mixtures thereof; (h) 3-, 4-,5-, 6-, 7-, 8-, 9-, 10- and 1,1-methyl-2-propyldodecanoic acid; andmixtures thereof; (i) 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-,2,3,10-, 2,3,11-, 2,3,12-, 2,4,5-, 2,4,7-, 2,4,9-, 2,4,11-, 2,4,12-,2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-, 2,6,7-,2,6,8-, 2,6,9-, 2,6,11-, 2,6,12-, 2,7,8-, 2,7,9-, 2,7,10-, 2,7,11-,2,7,12-, 2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,9,10-, 2,9,11-, 2,9,12-,2,10,11-, 2,10,12-, 2,11,12-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-,3,4,10-, 3,4,11-, 3,4,12-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,10-, 3,5,11-,3,5,12-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,7,8-,3,7,10-, 3,7,11-, 3,7,12-, 3,8,9-, 3,8,10-, 3,8,11-, 3,8,12-, 3,9,10-,3,9,11-, 3,9,12-, 3,10,11-, 3,10,12-, 3,11,12-, 4,5,6-, 4,5,7-, 4,5,8-,4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-,4,6,11-, 4,6,12-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-, 4,7,12-, 4,8,9-,4,8,10-, 4,8,11-, 4,9,10-, 4,9,11-, 4,9,12-, 4,10,11-, 4,10,12-,4,11,12-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-, 5,7,8-,5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-, 5,8,9-, 5,8,10-, 5,8,11-, 5,8,12-,5,9,10-, 5,9,11-, 5,9,12-, 5,10,11-, 5,10,12-, 5,11,12-, 6,7,8-, 6,7,9-,6,7,10-, 6,7,11-, 6,7,12-, 6,8,9-, 6,8,10-, 6,8,11-, 6,8,12-, 6,9,10-,6,9,11-, 6,9,12-, 6,10,11-, 6,10,12-, 6,11,12-, 7,8,9-, 7,8,10-,7,8,11-, 7,8,12-, 7,9,10-, 7,9,11-, 7,9,12-, 7,10,11-, 7,10,12-,7,11,12-, 8,9,10-, 8,9,11-, 8,9,12-, 8,10,11-, 8,10,12-, 8,11,12-,9,10,11-, 9,10,12-, 9,11,12- and 10,11,12-trimethyltridecanoic acid; andmixtures thereof; (j) 3-pentyl-4-propyl, 3-hexyl-4-ethyloctanoic acid;3-pentyl-4-methyl, 4-pentyl-5-methyl, 4-butyl-5-ethyl,5-butyl-6-ethyldecanoic acid; 5-butyl-6-methyl, 4-butyl-5-methyl,6-ethyl-7-propyl, 6-propyl-7-ethylundecanoic acid; 6,7-diethyl,7,8-diethyl, 7-methyl-8-propyl, 6-propyl-7-methyldodecanoic acid;7-methyl-8-ethyl, 6-ethyl-7-methyl, 8-methyl-8-ethyltridecanoic acid;and mixtures thereof; (k) mixtures of (a) to (j);
 2. A compositionaccording to claim 1, wherein said composition of matter comprises: atleast one of said branched carboxylic acid of (b); at least one of saidbranched carboxylic acid of (c); at least one of said branchedcarboxylic acid of (i); and optionally said branched carboxylic acid of(a).
 3. A composition according to claim 1, wherein said composition ofmatter comprises: at least one of said branched carboxylic acid of (b);at least one of said branched carboxylic acid of (c); at least one ofsaid branched carboxylic acid of (d); at least one of said branchedcarboxylic acid of (g); at least one of said branched carboxylic acid of(h); and optionally said branched carboxylic acid of (a).
 4. Acomposition according to claim 1, wherein said composition of mattercomprises: at least one of said branched carboxylic acid of (b); atleast one of said branched carboxylic acid of (c); at least one of saidbranched carboxylic acid of (d); at least one of said branchedcarboxylic acid of (g); at least one of said branched carboxylic acid of(h); at least one of said branched carboxylic acid of (i); andoptionally said branched carboxylic acid of (a).
 5. A compositionaccording to claim 1 comprising a mixture of said branched carboxylicacid, said mixture being substantially free from quaternary-carboncontaining branched carboxylic acid or their salts or derivatives.
 6. Acomposition according to claim 1 comprising a mixture of said branchedcarboxylic acids, further comprising a branched carboxylic acid havingan odd total number of carbon atoms.
 7. A composition according to claim1 comprising a mixture of said branched carboxylic acids, furthercomprising a branched carboxylic acid having an even total number ofcarbon atoms other than said branched carboxylic acids in claim
 1. 8. Acleaning composition comprising: (i) from about 0.05% to about 99.9%, byweight of a composition of matter according to claim 1; and (ii) fromabout 0.0001 to about 99.99%, by weight of conventional cleaningadditive.
 9. A skin care composition comprising: (i) from about 0.05% toabout 99.9%, by weight of a composition of matter according to claim 1;and (ii) from about 0.0001 to about 99.99%, by weight of a conventionalskin care additive.
 10. A personal cleansing composition comprising: (i)from about 0.05% to about 99.9%, by weight of a composition of matteraccording to claim 1; and (ii) from about 0.0001 to about 99.99%, byweight of a conventional personal cleansing additive.
 11. A paperarticle comprising at least about 0.0001% by weight of said compositionof matter according to claim
 1. 12. A composition according to claim 1comprising no more than about 0.1% aldehyde impurity.
 13. A compositionaccording to claim 1 comprising no more than about 0.1% unsaturatedimpurity.
 14. A composition according to claim 7 wherein said branchedcarboxylic acid having an odd total number of carbon atoms is selectedfrom the group consisting of: 15, 17, and 19 carbon atoms in total. 15.A composition according to claim 1 comprising at least six of saidbranched carboxylic acid.
 16. A composition according to claim 1comprising at least 20 of said branched carboxylic acid.